Polycarbonate resin composition

ABSTRACT

The invention relates to a polycarbonate resin composition, including (1) a colored composition that comprises two types of specifically-terminated aromatic polycarbonates along with an inorganic filler added thereto, (2) a composition that comprises a polycarbonate resin terminated with a specific phenoxy group, a functional group-having silicone compound and a core/shell-type grafted rubber-like elastomer, and (3) a composition that comprises a specifically-terminated aromatic polycarbonate-polyorganosiloxane copolymer, a specifically-terminated aromatic polycarbonate and a fibril-forming polytetrafluoroethylene.

TECHNICAL FIELD

The present invention includes first to third aspects all relating to apolycarbonate resin composition. Precisely, the first aspect of theinvention relates to a colored polycarbonate resin composition of goodflowability and impact resistance, of which the injection moldings areespecially glossy; the second aspect thereof relates to a polycarbonateresin composition of good impact resistance, moldability (meltflowability) and flame retardancy, not containing a halogen orphosphorus-containing flame retardant, and to its moldings; and thethird aspect of the invention relates to a polycarbonate resincomposition of good flowability, impact resistance and flame retardancy.

BACKGROUND ART

Having the advantages of mechanical strength (impact resistance), heatresistance and good electric properties, polycarbonate resins serve asengineering plastics and have many applications in various fields of,for example, electric and electronic appliances and automobile parts.Above all, colored polycarbonates are used, for example, for parts ofelectric and electronic appliances, parts of electrically-powered toolsand parts of cameras. Glass fibers serving as an inorganic filler areadded to such polycarbonate resins for improving the stiffness anddimensional stability of the resin articles, and they are known as glassfiber-reinforced polycarbonate resins.

Such glass fiber-reinforced polycarbonate resins are used for thin-wallmoldings these days, and it is desired to increase the flowability ofthe resins. Lowering the molecular weight of polycarbonate is effectivefor increasing the resin flowability, which, however, greatly lowers theimpact resistance of the resin articles.

To solve the problem, proposed are a composition that comprises a glassfiber-reinforced polycarbonate resin and an organosiloxane (JapanesePatent Publication No. 35929/1984, International Patent Publication No.501860/1982) and a polycarbonate-polyorganosiloxane copolymer reinforcedwith glass fibers (Japanese Patent Laid-Open No. 173061/1990). Thetechniques proposed are to improve the balance of the resin flowabilityand the impact resistance of the resin articles, but are stillunsatisfactory. Another problem with colored polycarbonate compositionsis that the glossiness of their injection moldings is not good whenordinary polycarbonate is used in the compositions.

The first aspect of the invention has been made in consideration of thesituation as above, and its object is to provide a colored polycarbonateresin composition of which the advantages are that its flowability isimproved not detracting from the impact resistance of the resinmoldings, and especially the glossiness of the injection moldings of theresin composition is extremely good.

As a rule, polycarbonate resins are self-extinguishable. However, insome fields of typically OA appliances, information and communicationappliances, and other electric and electronic appliances for householduse, required are polycarbonate resins of more improved flameretardancy. For these, various flame retardants are added topolycarbonate resins to meet the requirement.

For improving the flame retardancy of polycarbonate resins,halogen-containing flame retardants such as bisphenol A halides andhalogenated polycarbonate oligomers have been used along with a flameretardation promoter such as antimony oxide, as their flame-retardingability is good.

However, with the recent tendency toward safety living and environmentalprotection from discarded and incinerated wastes, the market requiresflame retardation with non-halogen flame retardants. As non-halogenflame retardants, phosphorus-containing organic flame retardants,especially organic phosphate compounds may be added to polycarbonateresin compositions, for which various methods have been proposed. Suchflame retardants, organic phosphate compounds serve also as aplasticizer, and polycarbonate resin compositions containing themexhibit excellent flame retardancy.

However, in order to make polycarbonate resins have good flameretardancy by adding thereto a phosphate compound, a relatively largeamount of the compound must be added to the resins. In general,polycarbonate resins require relatively high molding temperatures, andtheir melt viscosity is high. Therefore, for molding them intothin-walled and large-sized moldings, the molding temperature will haveto be higher. For these reasons, phosphate compounds often cause someproblems when added to such polycarbonate resins, though theirflame-retarding ability is good. For example, phosphate compounds oftencorrode molds used for molding resins containing them, and generate gasto have some unfavorable influences on the working environments and evenon the appearance of the moldings. Another problem with phosphatecompounds is that, when the moldings containing them are left under heator in high-temperature and high-humidity conditions, the compounds lowerthe impact strength of the moldings and yellow the moldings. Inaddition, polycarbonate resin compositions containing phosphatecompounds are not stable under heat, and therefore do not meet therecent requirement for recycling resin products. This is still anotherproblem with phosphate compounds.

Apart from the above, proposed is another technique of adding siliconecompounds to polycarbonate resins to make the resins have flameretardancy. In this, silicone compounds added to the resins do not givetoxic gas when fired. For example, (1) Japanese Patent Laid-Open No.139964/1998 discloses a flame retardant that comprises a silicone resinhaving a specific structure and a specific molecular weight.

(2) Japanese Patent Laid-Open Nos. 45160/1976, 318069/1989, 306265/1994,12868/1996, 295796/1996, and Japanese Patent Publication No. 48947/1991disclose silicone-containing, flame-retardant polycarbonate resincompositions.

The flame retardancy level of the products in (1) is high in somedegree, but the impact resistance thereof is often low. The technologyof (2) differs from that of (1) in that the silicones used in (2) do notact as a flame retardant by themselves, but are for improving thedropping resistance of resins, and some examples of silicones for thatpurpose are mentioned. Anyhow, in (2), the resins indispensably requirean additional flame retardant of, for example, phosphate compounds ormetal salts of Group 2 of the Periodic Table. Another problem with theflame-retardant polycarbonate resin compositions in (2) is that theflame retardant added thereto worsens the moldability and even thephysical properties of the resin compositions and their moldings.

Also known is a flame-retardant polycarbonate resin composition thatcomprises a polycarbonate-polyorganosiloxane copolymer-containing resin(this is one type of polycarbonate resin) and contains a fibril-formingpolytetrafluoroethylene (Japanese Patent Laid-Open No. 81620/1996). Eventhough its polyorganosiloxane content is low, falling within aspecifically defined range, the composition exhibits good flameretardancy. However, the composition is problematic in that its impactresistance characteristic of polycarbonate resin is often not goodthough its flame retardancy is good.

The second aspect of the invention has been made in consideration of thesituation as above, and its object is to provide a polycarbonate resincomposition of which the advantages are that its moldability, or thatis, melt flowability is improved not detracting from the impactresistance thereof characteristic of polycarbonate resin, its flameretardancy, heat resistance and recyclability are all good, and it canbe molded into thin-walled moldings that are lightweight and savenatural resources, and to provide such moldings of the composition.

Of various thermoplastic resins, polycarbonate resins have a highoxidation index and are therefore self-extinguishable. In general,however, the flame retardancy level needed in the field of OA appliancesand other electric and electronic appliances is high, concretely, V-0 asthe UL94 Standard. For making those appliances resistant to flames tothe desired level, therefore, flame retardant and flame retardationpromoter are added thereto. However, the additives lower the impactresistance and the heat resistance of the appliances.

In particular, flame-retardant materials of good flowability are desiredthese days for large-sized and thin-walled moldings for housings ofcopiers and printers. The flowability ofpolycarbonate-polyorganosiloxane copolymers could be increased byreducing the molecular weight thereof according to the technologymentioned above, but this is problematic in that the impact resistanceof the copolymers is low. On the other hand, the flowability ofpolycarbonate resins could also be increased by reducing the molecularweight thereof, but this is also problematic in that the flameretardancy and the impact resistance of the resins are low

The third aspect of the invention has been made in consideration of thesituation as above, and its object is to provide a polycarbonate resincomposition of good flowability, impact resistance and flame retardancy.

DISCLOSURE OF THE INVENTION

We, the present inventors have assiduously studied, and, as a result,have found that the object of the invention mentioned above can beattained by using an aromatic polycarbonate resin having a specificterminal group. On the basis of this finding, we have completed thefirst aspect of the invention.

Specifically, the first aspect of the invention is summarized asfollows:

1. A colored polycarbonate resin composition, which comprises 100 partsby weight of a polycarbonate resin comprising from 10 to 100% by weightof an aromatic polycarbonate (A) having a terminal group of thefollowing general formula (I-1):

wherein R¹ represents an alkyl group having from 10 to 35 carbon atoms,and from 0 to 90% by weight of an aromatic polycarbonate (B) having aterminal group of the following general formula (I-2):

wherein R² represents an alkyl group having from 1 to 9 carbon atoms, anaryl group having from 6 to 20 carbon atoms, or a halogen atom, and aindicates an integer of from 0 to 5,and from 5 to 150 parts by weight of an inorganic filler (C).

2. The polycarbonate resin composition of above 1, wherein the inorganicfiller (C) is glass fibers.

3. The polycarbonate resin composition of above 1 or 2, wherein R¹ informula (I-1) is a branched alkyl group having from 10 to 35 carbonatoms.

4. The polycarbonate resin composition of any of above 1 to 3, whereinthe polycarbonate resin has a viscosity-average molecular weight of from10,000 to 40,000.

5. Parts of electric and electronic appliances, parts ofelectrically-powered tools and parts of cameras, for which is used thepolycarbonate resin composition of any of above 1 to 4.

We, the inventors have further studied how to improve the impactresistance, the heat resistance, the recyclability and the moldabilityof polycarbonate resin in making the resin resistant to flames by thesilicone compound.

As a result, we have found that, when a specific polycarbonate resin iscombined selectively with <1> a specific minor silicon compound and aspecific rubber-like elastomer or with <2> a styrenic resin and aspecific fluororesin in preparing a polycarbonate resin composition,then the moldability and the flame retardancy of the resin compositionare significantly improved not detracting from the impact resistancethereof. On the basis of these findings, we have completed the secondaspect of the invention.

Specifically, the second aspect of the invention provides the following:

1. A polycarbonate resin composition, which comprises 100 parts byweight of a polycarbonate-based resin (A) that contains a polycarbonateresin terminated with a phenoxy group having an alkyl group with from 21to 35 carbon atoms, from 0.1 to 10 parts by weight of a functionalgroup-having silicone compound (B), and from 0.2 to 10 parts by weightof a core/shell-type, grafted rubber-like elastomer (C).

2. The polycarbonate resin composition of above 1, wherein thepolycarbonate-based resin (A) contains at least apolycarbonate-polyorganosiloxane copolymer and the polyorganosiloxanecontent of the polycarbonate-based resin is from 0.1 to 10% by weight.

3. The polycarbonate resin composition of above 1 or 2, which furthercontains from 0.02 to 5 parts by weight, relative to 100 parts by weightof the polycarbonate-based resin (A) therein, a polyfluoro-olefin resin(D).

4. A polycarbonate resin composition, which comprises 100 parts byweight of a resin mixture of from 1 to 99% by weight of apolycarbonate-based resin (A) that contains a polycarbonate resinterminated with an alkylphenol of which the alkyl group has from 21 to35 carbon atoms, and from 1 to 99% by weight of a styrenic resin (E),and from 0.01 to 5 parts by weight of a polyfluoro-olefin resin (D).

5. The polycarbonate resin composition of above 4, wherein thepolycarbonate-based resin (A) contains at least apolycarbonate-polyorganosiloxane copolymer and the polyorganosiloxanecontent of the polycarbonate-based resin is from 0.1 to 10% by weight.

6. The polycarbonate resin composition of above 4 or 5, wherein theresin mixture comprises from 70 to 98% by weight of thepolycarbonate-based resin (A) and from 2 to 30% by weight of arubber-modified styrenic resin as the component (E).

7. The polycarbonate resin composition of any of above 4 to 6, whichfurther contains from 0.1 to 10 parts by weight, relative to 100 partsby weight of the resin mixture of (A) and (E) therein, a functionalgroup-having silicone compound (B).

8. The polycarbonate resin composition of any of above 4 to 7, whichfurther contains from 1 to 100 parts by weight, relative to 100 parts byweight of the resin mixture of (A) and (E) therein, an inorganic filler(F).

9. Moldings of the polycarbonate resin composition of any of above 1 to8.

10. Housings or parts of electric and electronic appliances, for whichis used the polycarbonate resin composition of any of above 1 to 8.

We, the inventors have still further studied, and as a result, we havefound that the object of the invention mentioned above can be attainedby a polycarbonate resin composition comprising <1> an aromaticpolycarbonate resin that contains an aromaticpolycarbonate-polyorganosiloxane copolymer having an ordinary terminalgroup and an aromatic polycarbonate having a specific terminal group or<2> an aromatic polycarbonate resin that contains an aromaticpolycarbonate-polyorganosiloxane copolymer having a specific terminalgroup, and a specific polytetrafluoroethylene added thereto. On thebasis of these findings, we have completed the third aspect of theinvention.

Specifically, the third aspect of the invention is summarized asfollows:

1. A polycarbonate resin composition, which comprises 100 parts byweight of an aromatic polycarbonate resin that contains an aromaticpolycarbonate-polyorganosiloxane copolymer (A) having a terminal groupof the following general formula (III-1):

wherein R¹ represents an alkyl group having from 1 to 9 carbon atoms, anaryl group having from 6 to 20 carbon atoms, or a halogen atom, and aindicates an integer of from 0 to 5,and an aromatic polycarbonate (B) having a terminal group of thefollowing general formula (III-2):

wherein R² represents an alkyl group having from 21 to 35 carbon atoms,and from 0.05 to 1 part by weight of a fibril-formingpolytetrafluoroethylene (C) having a mean molecular weight of at least500,000.

2. The polycarbonate resin composition of above 1, wherein the aromaticpolycarbonate resin that contains the components (A) and (B) has aviscosity-average molecular weight of from 10,000 to 40,000.

3. The polycarbonate resin composition of above 1 or 2, wherein thepolyorganosiloxane content of the component (A) is from 0.1 to 2% byweight of the aromatic polycarbonate resin that contains the components(A) and (B).

4. The polycarbonate resin composition of any of above 1 to 3, whereinthe ratio of the component (B) is at least 10% by weight of the aromaticpolycarbonate resin that contains the components (A) and (B).

5. A polycarbonate resin composition, which comprises 100 parts byweight of an aromatic polycarbonate resin that contains an aromaticpolycarbonate-polyorganosiloxane copolymer (D) having a terminal groupof the following general formula (III-2′):

wherein R² represents an alkyl group having from 21 to 35 carbon atoms,and from 0.05 to 1 part by weight of a fibril-formingpolytetrafluoroethylene (C) having a mean molecular weight of at least500,000.

6. The polycarbonate resin composition of above 5, wherein the aromaticpolycarbonate resin that contains the component (D) has aviscosity-average molecular weight of from 10,000 to 40,000.

7. The polycarbonate resin composition of above 5 or 6, wherein thepolyorganosiloxane content of the component (D) is from 0.1 to 2% byweight of the aromatic polycarbonate resin that contains the component(D).

8. Housings or parts of electric and electronic appliances, for which isused the polycarbonate resin composition of any of above 1 to 7.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a perspective view of a tool for holding a test piece thereonfor evaluating the grease resistance of the composition of the secondaspect of the invention.

BEST MODES OF CARRYING OUT THE INVENTION

The invention is described in detail hereinunder.

[I] First Aspect of the Invention:

The component (A) of the polycarbonate resin composition of the firstaspect of the invention (in this section, the “first aspect of theinvention” will be simply referred to as “the invention”) is an aromaticpolycarbonate having a terminal group of formula (I-1) mentioned above.In formula (I-1), R¹ represents an alkyl group having from 10 to 35carbon atoms, and it may be linear or branched.

The aromatic polycarbonate may be produced in any known method ofgenerally reacting a biphenol with a polycarbonate precursor such asphosgene or a carbonate compound. Concretely, for example, it may beproduced by reacting a diphenol with a polycarbonate precursor such asphosgene or by interesterifying a carbonate precursor such as diphenylcarbonate with a diphenol, in a solvent such as methylene chloride inthe presence of a known acid receptor and a long-chain alkylphenolserving as a terminal stopper of the following formula (I-3):

wherein R¹ has the same meaning as above,optionally with adding a branching agent to the reaction system.

Various types of diphenols are known, and2,2-bis(4-hydroxyphenyl)propane (generally referred to as bisphenol A)is favorable to the invention. Except bisphenol A, other diphenolsusable herein are, for example, bis(hydroxyaryl)alkanes such asbis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-tert-butylphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane,2,2-bis(4-hydroxy-3,5-tetramethylphenyl)propane,2,2-bis(4-hydroxy-3-chlorophenyl)propane,2,2-bis(4-hydroxy-3,5-tetrachlorophenyl)propane,2,2-bis(4-hydroxy-3,5-tetrabromophenyl)propane;bis(hydroxyaryl)arylalkanes such as2,2-bis(4-hydroxyphenyl)phenylmethane,bis(4-hydroxyphenyl)naphthylmethane; bis(hydroxyaryl)cycloalkanes suchas 1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane; dihydroxyarylethers such as 4,4′-dihydroxyphenyl ether,4,4′-dihydroxy-3,3′-dimethylphenyl ether; dihydroxydiaryl sulfides suchas 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfide; dihydroxydiaryl sulfoxides such as 4,4′-dihydoxydiphenylsulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide;dihydroxydiaryl sulfones such as 4,4′-dihydoxydiphenyl sulfone,4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone; and dihydroxydiphenylssuch as 4,4′-dihydroxydiphenyl. Singly or as combined, one or more ofthese diphenols may be used for the reaction.

The carbonate compound includes, for example, diaryl carbonates such asdiphenyl carbonate; and dialkyl carbonates such as dimethyl carbonate,diethyl carbonate.

For the terminal stopper, used are long-chain monoalkylphenols offormula (I-3), of which p-alkylphenols are especially preferred for useherein. In the formula, R¹ represents an alkyl group having from 10 to35 carbon atoms, and it may be linear or branched but is preferablybranched. R¹ is preferably an alkyl group having from 12 to 24 carbonatoms.

If the number of carbon atoms constituting the alkyl group is 9 or less,it is unfavorable since the flowability of the aromatic polycarbonateresin is low; but if 36 or more, it is also unfavorable since the heatresistance of the resin composition gradually lowers.

Singly or as combined, one or more of the long-chain monoalkylphenolsmay be used herein. Not interfering with the effect of the invention,the long-chain monoalkylphenol may be combined with any otheralkylphenol of which the alkyl group has at most 9 carbon atoms.

As the case may be, the hydroxyl group of the diphenol may remain in thepolycarbonate not completely terminated in the manner specificallydefined herein, and the terminal fraction may be at least about 60%.

For the optional branching agent, for example, usable is a compoundhaving at least three functional groups such as1,1,1-tris(4-hydroxyphenyl)ethane,α,α′α″-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene,1-[α-methyl-α-(4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis(4″-hydroxyphenyl)ethyl]benzene,phloroglucine, trimellitic acid, isatin-bis(o-cresol).

The component (B) of the polycarbonate resin composition of the firstaspect of the invention is an aromatic polycarbonate having a terminalgroup of formula (I-2). The aromatic polycarbonate is not specificallydefined, and it may be readily produced by reacting a diphenol withphosgene or a carbonate compound.

Concretely, for example, it may be produced by reacting a diphenol witha carbonate precursor such as phosgene or by interesterifying acarbonate precursor such as diphenyl carbonate with a diphenol, in asolvent such as methylene chloride in the presence of a catalyst such astriethylamine and a terminal stopper.

The diphenol may be the same as or different from that mentionedhereinabove. The polycarbonate may be a homopolymer for which one andthe same diphenol is used, or a copolymer for which two or moredifferent types of diphenols are used. Further, it may also be athermoplastic random-branched polycarbonate for which the diphenol iscombined with a polyfunctional aromatic compound.

Examples of the dicarbonate compound are diaryl carbonates such asdiphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate ordiethyl carbonate.

For the terminal stopper, used is a monophenol compound of the followinggeneral formula (I-4):

wherein R² and a have the same meanings as above. Preferably, it is apara-substituted monophenol. Concretely, it includes, for example,phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol,p-nonylphenol, p-tert-amylphenol.

The polycarbonate resin to be in the polycarbonate resin composition ofthe invention comprises the components (A) and (B). Regarding theirblend ratio, the amount of the component (A) is from 10 to 100% byweight, and that of the component (B) is from 0 to 90% by weight. If theamount of the component (A) is smaller than 10% by weight, it isunfavorable since the flowability of the resin composition of theinvention is low and the moldings of the composition are not glossy.

The viscosity-average molecular weight (Mv) of the polycarbonate resinpreferably falls between 10,000 and 40,000, more preferably between12,000 and 30,000, even more preferably between 15,000 and 25,000. Ifthe molecular weight of the resin is too low, the impact resistance ofthe resin moldings will be low; but if too high, the resin compositionwill be difficult to mold.

Various types of inorganic fillers are known for the component (C) to beadded to the polycarbonate resin in the invention, and they are forincreasing the mechanical strength and improving the dimensionalstability of the polycarbonate resin composition or for increasing theamount of the resin composition.

The inorganic filler includes, for example, potassium titanate whiskers,mineral fibers (e.g., rock wool), glass fibers, carbon fibers, metalfibers (e.g., stainless steel fibers), aluminium borate whiskers,silicon nitride whiskers, boron fibers, tetrapod zinc oxide whiskers,talc, clay, mica, pearl mica, aluminium leaf, alumina, glass flakes,glass beads, glass balloons, carbon black, graphite, calcium carbonate,calcium sulfate, calcium silicate, titanium oxide, zinc oxide, silica,asbestos, and quarts powder. These inorganic fillers may be previouslysurface-treated or may not. The surface-treating agent includes, forexample, silane coupling agents, higher fatty acids, metal salts offatty acids, unsaturated organic acids, organic titanates, resin acids,and polyethylene glycols. With any of these, the inorganic fillers maybe chemically or physically surface-treated.

Of the inorganic fillers mentioned above, preferred for use herein areglass fibers and carbon fibers.

For the glass fibers for use herein, any of alkali glass, low-alkaliglass or non-alkali glass is preferred. The length of the glass fiberspreferably falls between 0.1 and 8 mm, more preferably between 0.3 and 6mm. Their diameter may fall between 0.1 and 30 μm, but preferablybetween 0.5 and 25 μm. The glass fibers are not specifically defined inpoint of their morphology, and they may be in any form of rovings,milled fibers or chopped fibers. Singly or as combined, one or moredifferent types of such glass fibers may be used herein. Preferably, theglass fibers are treated with a surface-treating agent and thenprocessed with a suitable sizing agent for enhancing the adhesivenessthereof to polycarbonate resin. The surface-treating agent includes, forexample, silane coupling agents such as aminosilanes, epoxysilanes,vinylsilanes, acrylic silanes; titanate coupling agents, and aluminium,chromium, zirconium or boron-containing coupling agents. Of those,preferred for use herein are silane coupling agents and titanatecoupling agents, and more preferred are silane coupling agents. Fortreating the glass fibers with such a surface-treating agent, the methodis not specifically defined and may be any conventional one. Forexample, employable are an aqueous solution method, an organic solventmethod and a spraying method. The sizing agent includes, for example,urethane compounds, acrylic compounds, acrylonitrile-styrene copolymersand epoxy compounds, any of which are usable herein. For processing theglass fibers with such a sizing agent, the method is not specificallydefined and may be any conventional one. For example, employable is anymethod of dipping, roller-coating, blasting, casting or spraying.

The carbon fibers for use herein may be produced from cellulose fibers,acrylic fibers, lignin, or petroleum or coal-type special pitchgenerally by firing them. Various types of such carbon fibers are known,including, for example, flame-retardant, carbonaceous or graphitic ones.The length of the carbon fibers generally falls between 0.01 and 10 mm,and the diameter thereof may fall between 5 and 15 μm. The morphology ofthe carbon fibers is not specifically defined, including, for example,rovings, milled fibers and chopped strands. The carbon fibers may besurface-treated with epoxy resin or urethane resin for enhancing theiraffinity for polycarbonate resin.

The amount of the inorganic filler to be in the resin composition of theinvention is from 5 to 150 parts by weight, but preferably from 10 to 80parts by weight, relative to 100 parts by weight of the polycarbonateresin therein. If it is smaller than 5 parts by weight, the stiffness ofthe resin composition is low and the dimensional stability thereof isalso low. If larger than 150 parts by weight, it is unfavorable sincethe resin composition is difficult or impossible to knead. Within thepreferred range, the inorganic filler is effective for more enhancingthe impact resistance of the resin moldings.

Not interfering with the object of the invention, the polycarbonateresin composition may contain from 100 to 5,000 ppm of a colorant,further optionally other additives and other synthetic resins orelastomers.

The additives are, for example, antioxidants such as hindered phenols,phosphorus-containing compounds (e.g., phosphites, phosphates), amines;UV absorbents such as benzotriazoles, benzophenones; optical stabilizerssuch as hindered amines; internal lubricants such as aliphaticcarboxylates, paraffins, silicone oil, polyethylene wax; and moldrelease agents, flame retardants, flame retardation promoters,antistatic agents, colorants.

The additional synthetic resins are, for example, polyethylene resins,polypropylene resins, polystyrene resins, AS resins(acrylonitrile-styrene copolymers), ABS resins(acrylonitrile-butadiene-styrene copolymers), polymethyl methacrylateresins. The elastomers are, for example, isobutylene-isoprene rubber,styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomers.

The components mentioned above may be formulated and kneaded in anyordinary method. For it, example, usable are any of ribbon blenders,drum tumblers, Henschel mixers, Banbury mixers, single-screw extruders,double-screw extruders, cokneaders, and multi-screw extruders. Whilekneaded, they may be heated generally at 240 to 320° C.

The thus-obtained, colored polycarbonate resin composition may be moldedin any known method. For example, it may be molded in any mode ofinjection molding, blow molding, extrusion molding, compression molding,calender molding or spin molding to give colored moldings such as partsof electric and electronic appliances, parts of electrically-poweredtools and parts of cameras.

The first aspect of the invention is described more concretely withreference to its Production Examples, Examples and Comparative Examples,which, however, are not intended to restrict the scope of the firstaspect of the invention.

[Preparation of Alkylphenol (a)]

Starting compounds, 300 parts by weight of phenol and 105 parts byweight of 1-eicosene/1-docosene/1-tetracosene (composition ratio,53.3/40.2/6.5 by mol %) in a molar ratio of phenol/olefin=9/1, and 10.5parts by weight of a catalyst, strong-acid polystyrenic sulfonate cationresin (Amberlyst 15 from Rohm and Haas) were put into a reactor equippedwith a baffle and a stirring blade, and reacted at 120° C. with stirringfor 3 hours. After the reaction, the mixture was purified throughdistillation under reduced pressure to obtain an alkylphenol (a). In theresulting alkylphenol (a), the alkyl group had 21 carbon atoms onaverage and was branched.

[Preparation of Alkylphenol (b)]

In the same manner as in preparing the alkylphenol (a), an alkylphenol(b) was prepared for which, however, the olefin used was 1-docosene, itsamount was 110 parts by weight, the molar ratio of phenol/olefin was 9/1and the amount of the catalyst used was 11 parts by weight. In thealkylphenol (b), the alkyl group had 22 carbon atoms and was branched.

[Production of Polycarbonate Oligomer]

60 kg of bisphenol A was dissolved in 400 liters of aqueous wt. % sodiumhydroxide solution to prepare an aqueous solution of bisphenol A insodium hydroxide.

Next, the aqueous solution of bisphenol A in sodium hydroxide kept atroom temperature was fed into a tubular reactor having an inner diameterof 10 mm and a length of 10 m, at a flow rate of 138 liters/hr via anorifice plate of the reactor, along with methylene chloride thereintovia the plate at a flow rate of 69 liters/hr, while, at the same time,phosgene was also thereinto at a flow rate of 10.7 kg/hr, and they werecontinuously reacted for 3 hours. The tubular reactor used herein is ajacketed tube, in which cooling water was circulated through the jacketso as to keep the reaction mixture discharge at 25° C. The pH of thedischarge was controlled to fall between 10 and 11.

The thus-obtained reaction mixture was kept static for phase separation.Its aqueous phase was removed, and its methylene chloride phase (220liters) was collected to obtain a polycarbonate oligomer (concentration,317 g/liter). The degree of polymerization of the polycarbonate oligomerfell between 2 and 4, and the chloroformate concentration thereof was0.7 normalities.

[Production of Polycarbonate A₁]

10 liters of the polycarbonate oligomer obtained in the above was putinto a 50-liter reactor equipped with a stirrer, and 136 g ofp-dodecylphenol (from Yuka Schenectady, branched) was dissolved therein.Next, aqueous sodium hydroxide solution (sodium hydroxide 53 g, water 1liter) and 5.8 ml of triethylamine were added thereto and reacted bystirring at 300 rpm for 1 hour. Then, the system was mixed with asolution of bisphenol A in sodium hydroxide (bisphenol A 720 g, sodiumhydroxide 412 g, water 5.5 liters), 8 liters of methylene chloride wasadded thereto, and these were reacted by stirring at 500 rpm for 1 hour.After the reaction, 7 liters of methylene chloride and 5 liters of waterwere added to the system, and stirred at 500 rpm for 10 minutes. Afterstirring it was stopped, the system was kept static for phase separationinto an organic phase and an aqueous phase. The resulting organic phasewas washed with 5 liters of an alkali (0.03-N NaOH), 5 liters of an acid(0.2-N HCl) and 5 liters of water (twice) in that order. Next, methylenechloride was evaporated away to obtain a flaky polymer (polycarbonateA₁). The alkylphenoxy terminal fraction of the polymer was 99.5%, andthe viscosity-average molecular weight thereof was 20,000.

[Production of Polycarbonate A₂]

In the same manner as in producing the polycarbonate A₁, a polycarbonateA₂ was produced, for which, however, 202 g of the alkylphenol (a) wasused in place of p-dodecylphenol. The alkylphenoxy terminal fraction ofthe polymer was 99.0%, and the viscosity-average molecular weightthereof was 20,000.

[Production of Polycarbonate A₃]

In the same manner as in producing the polycarbonate A₁, a polycarbonateA₃ was produced, for which, however, 209 g of the alkylphenol (b) wasused in place of p-dodecylphenol. The alkylphenoxy terminal fraction ofthe polymer was 99.0%, and the viscosity-average molecular weightthereof was 20,000.

[Production of Polycarbonate B₁]

In the same manner as in producing the polycarbonate A₁, a polycarbonateB₁ was produced, for which, however, 77.6 g of p-tert-butylphenol wasused in place of p-dodecylphenol. The p-tert-butylphenoxy terminalfraction of the polymer was 99.5%, and the viscosity-average molecularweight thereof was 20,000.

The viscosity of the polycarbonate in methylene chloride at 20° C. wasmeasured with an Ubbelohde's viscometer, and the intrinsic viscosity [η]thereof was derived from it. The viscosity-average molecular weight (Mv)of the polycarbonate was calculated according to the following equation:[η]=1.23×10⁻⁵ Mv^(0.83).

EXAMPLES I-1 TO I-12, AND COMPARATIVE EXAMPLES I-1 to I-3

2,000 ppm of a colorant, carbon black (Mitsubishi Carbon Sharp 1000 fromMitsubishi Chemical) was added to the polycarbonate obtained in theabove-mentioned Production Example, and glass fibers (MA-409C from AsahiFiber Glass) were added thereto in different ratios as in Table I-1.This was kneaded in a vented double-screw extruder (TEM-35B from ToshibaKikai) at 300° C., and pelletized through it. In Examples I-2, 3, 6, 7,10, 11 and Comparative Examples I-2, 3, 200 ppm of an antioxidant(phosphorus-containing antioxidant PEP36 from Asahi Denka Kogyo) wasadded to the composition. In Examples I-2, 6, 10 and Comparative ExampleI-3, 2,000 ppm of a lubricant (SH200 from Toray Dow-Corning) was addedto the composition.

According to the method mentioned below, the spiral flow length (SFL) ofthe pellets was measured. At a cylinder temperature of 300° C. and at amold temperature of 80° C., the pellets were molded into test pieces,and their gloss and Izod impact strength were measured. The data aregiven in Table I-1. In the Table, “Example I-1” is simply designated as“Example 1”, and the same shall apply to Comparative Examples.

(1) SFL:

The pellets are injection-molded to give a melt flow of 10 mm wide and 3mm thick. The injection pressure is 80 kg/cm² (7.84 MPa), the resintemperature is 300° C., and the mold temperature is 80° C.

(2) Gloss:

The 60-degree mirror-face gloss of each test piece is measured accordingto JIS K 7105.

(3) Izod Impact Strength:

Measured according to JIS K 7110. Five samples of the same resincomposition are tested in the same manner and their data are averaged.

TABLE I-1 Glass Polycarbonate Fibers Izod Impact A B amount SFL Strengthwt. % wt. % (wt.pts.) cm Gloss kJ/m² Example 1 A₁ (100) 0 11 58 73 6Example 2 A₁ (100) 0 25 49 43 9 Example 3 A₁ (100) 0 43 45 31 11 Example4 A₁ (85)  15 43 43 29 11 Example 5 A₂ (100) 0 11 72 76 6 Example 6 A₂(100) 0 25 55 48 10 Example 7 A₂ (100) 0 43 40 35 12 Example 8 A₂ (85) 15 43 36 31 11 Example 9 A₃ (100) 0 11 73 77 6 Example 10 A₃ (100) 0 2556 49 10 Example 11 A₃ (100) 0 43 40 36 12 Example 12 A₃ (85)  15 43 3632 11 Comp. Ex. 1 0 100 11 38 59 6 Comp. Ex. 2 0 100 25 34 35 8 Comp.Ex. 3 0 100 43 31 17 11

From Table I-1, it is understood that the flowability and the gloss ofthe samples of Examples are both better than those of the samples ofComparative Examples though the impact resistance of the former does notdiffer from that of the latter.

[II] Second Aspect of the Invention:

The polycarbonate resin composition of the second aspect of theinvention (in this section, the “second aspect of the invention” will besimply referred to as “the invention”) comprises 100 parts by weight ofa polycarbonate-based resin (A) that contains a polycarbonate resinterminated with a phenoxy group having an alkyl group with from 21 to 35carbon atoms, from 0.1 to 10 parts by weight of a functionalgroup-having silicone compound (B), and from 0.2 to 10 parts by weightof a core/shell-type, grafted rubber-like elastomer (C).

The polycarbonate resin composition of the invention is characterized inthat its constituent component (A) is a polycarbonate-based resin thatcontains a polycarbonate resin terminated with a phenoxy group having analkyl group with from 21 to 35 carbon atoms (this will be hereinafterreferred to as a terminal-modified PC).

The polycarbonate resin terminated with a phenoxy group having an alkylgroup with from 21 to 35 carbon atoms can be obtained by using analkylphenol having an alkyl group with from 21 to 35 carbon atoms as theterminal stopper in producing it. The alkylphenol is not specificallydefined, including, for example, docosylphenol, tetracosylphenol,hexacosylphenol, octacosylphenol, triacontylphenol, dotriacontylphenoland tetratriacontylphenol. Singly or as combined, one or more of thesephenols may be used herein. Not interfering with the effect of theinvention, the alkylphenol may be combined with any other phenol such asan alkylphenol having at most 20 carbon atoms.

The alkyl group in the alkylphenol may be at any of o-, m- or p-positionrelative to the hydroxyl group therein, but is preferably at p-position.The alkyl group may be linear or branched.

In any of the polycarbonate-based resin mentioned below, the specificterminal-modified PC may be prepared, for example, through reaction of adiphenol with phosgene or a carbonate compound using the alkylphenol asthe terminal stopper for controlling the molecular weight of theresulting polymer.

For example, it is prepared by reacting a diphenol with phosgene or apolycarbonate oligomer in a methylene chloride solvent in the presenceof a triethylamine catalyst and a phenol having an alkyl group with from21 to 35 carbon atoms. In this, the phenol having an alkyl group withfrom 21 to 35 carbon atoms terminates to modify one or both terminals ofthe polycarbonate resin. The terminal modification in the polycarbonateresin is at least 20%, preferably at least 50% of all the terminals ofthe resin. Accordingly, the other terminal not specifically modified inthe polycarbonate resin is a hydroxyl terminal group or a groupterminated with any other terminal stopper mentioned below.

The other terminal stoppers are phenols generally used in polycarbonateresin production, including, for example, phenol, p-tert-butylphenol,p-tert-octylphenol and p-cumylphenol. However, if such phenols only areused, it is impossible to obtain the resin composition of the inventionhaving both good moldability and good impact resistance.

The viscosity-average molecular weight of the terminal-modified PC inthe component (A) of the polycarbonate resin composition of theinvention generally falls between 10,000 and 40,000, but preferablybetween 12,000 and 30,000.

The component (A) of the polycarbonate resin composition of theinvention contains the specific terminal-modified PC, polycarbonateresin terminated with a phenoxy group having an alkyl group with from 21to 35 carbon atoms. In this, the specific terminal-modified PC may bealone or may be combined with any other ordinary polycarbonate resin.The specific terminal-modified PC content of the component is notspecifically defined, generally at least 20% by weight, but preferablyat least 50% by weight, more preferably at least 70% by weight inconsideration of all the terminals of the polycarbonate-based resin ofthe component (A) for better moldability (melt flowability) of the resincomposition. The content may be suitably determined, depending on theratio of the phenoxy group having an alkyl group with from 21 to 35carbon atoms in the terminal-modified PC, the type of the other terminalof the modified PC, the type of the terminal of the other polycarbonateresin combined with the modified PC, and the melt flowability of theresin composition containing the modified PC.

The polycarbonate resins to constitute the component (A) of thepolycarbonate resin composition of the invention are not specificallydefined, including those known in the art. Generally used herein arearomatic polycarbonates to be produced from diphenols and carbonateprecursors. For example, herein used are polycarbonates as produced byreacting a diphenol with a carbonate precursor in a solution method orin a melt method, such as those produced through reaction of a diphenolwith phosgene or through interesterification of diphenyl carbonate witha diphenol.

Various diphenols are usable, typically including2,2-bis(4-hydroxyphenyl)propane [bisphenol A],bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxydiphenyl,bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl) oxide,bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone,bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether, andbis(4-hydroxyphenyl) ketone.

As the diphenols for use herein, preferred arebis(hydroxyphenyl)alkanes, especially those consisting essentially ofbisphenol A. The carbonate precursors for use in the invention include,for example, carbonyl halides, carbonyl esters, and haloformates,concretely, phosgene, diphenol dihaloformates, diphenyl carbonate,dimethyl carbonate, and diethyl carbonate. Other diphenols such ashydroquinone, resorcinol, and catechol are also usable in the invention.The diphenols mentioned herein may be used either singly or as combined.

The polycarbonate resin may have a branched structure, for which thebranching agent includes, for example,1,1,1-tris(4-hydroxyphenyl)ethane,α,α′,α″-tris(4-hyroxyphenyl)-1,3,5-triisopropylbenzene, phloroglucine,trimellitic acid, and isatin-bis(o-cresol). For controlling themolecular weight of the polycarbonate resin, for example, employable arephenol, p-t-butylphenol, p-t-octylphenol, p-cumylphenol, andalkylphenols having an alkyl group with from 21 to 35 carbon atoms suchas those mentioned above.

The polycarbonate resin composition of the invention is characterized inthat it contains the terminal-modified PC which is terminated at leastwith the molecular weight-controlling agent, alkylphenol having an alkylgroup with from 21 to 35 carbon atoms.

The polycarbonate resin and the terminal-modified PC for use in theinvention may be polyester-polycarbonate copolymers to be producedthrough polymerization of polycarbonates in the presence of an esterprecursor, such as a difunctional carboxylic acid (e.g., terephthalicacid, polymethylenedicarboxylic acid) or its ester-forming derivative,or may also be mixtures of different types of polycarbonate resins.

One typical example of other polycarbonate copolymers also usable hereinis a polycarbonate-polyorganosiloxane copolymer (hereinafter abbreviatedas PC-PDMS copolymer). The PC-PDMS copolymer comprises a polycarbonatemoiety and a polyorganosiloxane moiety. For example, this may beprepared by dissolving a polycarbonate oligomer and a polyorganosiloxanehaving a reactive group at its terminal (this is to form thepolyorganosiloxane moiety in the copolymer, and includes, for example,polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane) ina solvent of, for example, methylene chloride, adding thereto an aqueoussolution of bisphenol A containing sodium hydroxide, and reacting themin a mode of interfacial polycondensation in the presence of a catalystof, for example, triethylamine. The PC-PDMS copolymer is disclosed in,for example, Japanese Patent Laid-Open Nos. 292359/1991, 202465/1992,81620/1996, 302178/1996 and 7897/1998.

In the PC-PDMS copolymer, the degree of polymerization of thepolycarbonate moiety preferably falls between 3 and 100 or so, and thedegree of polymerization of the polydimethylsiloxane moiety preferablyfalls between 2 and 500 or so. The polydimethylsiloxane content of thePC-PDMS copolymer (including its by-product, bisphenol A polycarbonate)may generally fall between 0.2 and 30% by weight, but preferably between0.3 and 20% by weight. The viscosity-average molecular weight of thepolycarbonate resin and the polycarbonate copolymer such as PC-PDMScopolymer for use in the invention may fall generally between 10,000 and100,000, but preferably between 11,000 and 40,000, more preferablybetween 12,000 and 30,000. The viscosity of the resin or the copolymerin methylene chloride at 20° C. is measured with an Ubbelohde'sviscometer, and the intrinsic viscosity [η] thereof is derived from it.The viscosity-average molecular weight (Mv) of the resin or thecopolymer is calculated according to the following equation:[η]=1.23×10⁻⁵ Mv ^(0.83).

The component (A) of the polycarbonate resin composition of theinvention may be a mixed resin of the above-mentioned, specificterminal-modified polycarbonate resin, PC-PDMS copolymer and bisphenol Apolycarbonate. The polydimethylsiloxane content of the component (A) ofthis case is defined to fall between 0.1 and 10% by weight, preferablybetween 0.3 and 5% by weight of the mixed resin to be thepolycarbonate-based resin for the component (A)

(B) Functional Group-Having Silicone Compound:

The functional group-having silicone compound for the component (B) ofthe polycarbonate resin composition of the second aspect of theinvention is a functional group-having (poly)organosiloxane. Preferably,it is a polymer or copolymer having a basic structure of a formula:R¹ _(a)R² _(b)SiO_((4-a-b)/2)wherein R¹ represents a functional group, R² represents a hydrocarbonresidue having from 1 to 12 carbon atoms, and 0<a≦3, 0≦b<3, and 0<a+b≦3.The functional group includes, for example, an alkoxy group, an aryloxygroup, a polyoxyalkylene group, a hydride residue, a hydroxyl group, acarboxyl group, a silanol group, an amino group, a mercapto group, anepoxy group.

The silicone compound may have different functional groups; or siliconecompounds each having a different functional group may be combined forthe component (B). In the basic structure of the functional group-havingsilicone compound, the ratio of functional group (R¹)/hydrocarbonresidue (R²) generally falls between 0.1 and 3 or so, but preferablybetween 0.3 and 2 or so.

The silicone compound is liquid or powdery, but is preferably welldispersible in the other constituent components while they are kneadedin melt. One example of the compound is liquid and has a kinematicviscosity at room temperature of from 10 to 500,000 mm²/sec or so. Thepolycarbonate resin composition of the invention is characterized inthat the silicone compound uniformly disperses therein even when it isliquid, and bleeds little out of the composition being molded and out ofthe moldings of the composition.

The resin composition may contain from 0.1 to 10 parts by weight,preferably from 0.2 to 5 parts by weight of the functional group-havingsilicone compound, relative to 100 parts by weight of thepolycarbonate-based resin (A) therein. If the amount of the siliconecompound therein is smaller than 0.1 parts by weight, the resincomposition could not be resistant to flames; but even if larger than 10parts by weight, the silicone compound could no more augment its effect.In case where the polycarbonate-based resin in the resin compositioncontains PC-PDMS copolymer, the functional group-having siliconecompound content of the resin composition may be suitably determined inconsideration of the overall silicone content of the resin composition.In that case, since the resin composition contains some silicone inaddition to the functional group-having silicone compound, thefunctional group-having silicone compound content of the resincomposition may be reduced. Another advantage of the case is that thelevel of the flame retardancy of the resin composition is kept high evenwhen the overall silicone content of the resin composition is lowered.

If non-functional silicone compounds with ordinary alkyl groups such asdimethylsilicone are used in place of the functional group-havingsilicone compound for the component (B), they are ineffective forimproving the flame retardancy of the resin composition as inComparative Examples mentioned below.

(C) Core/Shell-type, Grafted Rubber-like Elastomer:

For the component (C) of the polycarbonate resin composition of theinvention, the core/shell-type, grafted rubber-like elastomer has atwo-layered structure composed of a core and a shell, in which the coreis of a flexible rubber material and the shell that covers the core isof a hard resin material. As a whole, the elastomer itself is powdery orgranular. After blended with polycarbonate resin in melt, thecore/shell-type, grafted rubber-like elastomer of that type mostly keepsits original powdery or granular condition. Since the graftedrubber-like elastomer mostly keeps its original powdery or granularcondition after having been blended with the resin melt, it uniformlydisperses in the resin composition and is effective for preventing themoldings of the resin composition from being troubled by surface layerpeeling.

Known are various core/shell-type, grafted rubber-like elastomers thatare usable herein. Commercially-available products of such elastomersinclude, for example, Hiblen B621 (from Nippon Zeon), KM-330 (from Rohm& Haas), Metablen W529, Metablen S2001, Metablen C223, Metablen B621(all from Mitsubishi Rayon).

Above all, for example, preferred are those to be produced throughpolymerization of one or more vinylic monomers in the presence of arubber-like polymer obtained from monomers of essentially alkylacrylates or alkyl methacrylates with dimethylsiloxane. In the alkylacrylates and acryl methacrylates, the alkyl group preferably has from 2to 10 carbon atoms. Concretely, the acrylates and methacrylates include,for example, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, andn-octyl methacrylate. One example of the rubber-like polymers that areobtained from monomers of essentially those alkyl (meth)acrylates is apolymer to be prepared through reaction of at least 70% by weight of analkyl acrylate with at most 30% by weight of any other copolymerizablevinylic monomer such as methyl methacrylate, acrylonitrile, vinylacetate, styrene. To prepare the polymer, a polyfunctional monomerserving as a crosslinking agent, such as divinylbenzene, ethylenedimethacrylate, triallyl cyanurate or triallyl isocyanurate, may besuitably added to the polymerization system.

The vinylic monomers to be polymerized in the presence of such arubber-like polymer include, for example, aromatic vinyl compounds suchas styrene, α-methylstyrene; acrylates such as methyl acrylate, ethylacrylate; and methacrylates such as methyl methacrylate, ethylmethacrylate. One or more these monomers may be (co)polymerized, ascombined, or may be copolymerized with any other vinylic monomers suchas vinyl cyanides (e.g., acrylonitrile, methacrylonitrile), and vinylesters (e.g., vinyl acetate, vinyl propionate). The (co)polymerizationmay be effected in any known method of, for example, bulkpolymerization, suspension polymerization, or emulsion polymerization.Especially preferred is emulsion polymerization.

It is desirable that the core/shell-type, grafted rubber-like elastomersthus produced in the manner mentioned above contain at least 20% byweight of the rubber-like polymer moiety. Typical examples of thecore/shell-type, grafted rubber-like elastomers are MAS resin elastomerssuch as graft copolymers of styrene and methyl methacrylate with from 60to 80% by weight of n-butyl acrylate. Other examples are compositerubber grafted copolymers to be prepared through graft copolymerizationof a composite rubber with at least one vinylic monomer, in which thecomposite rubber comprises from 5 to 95% by weight of a polysiloxanerubber component and from 5 to 95% by weight of apolyacryl(meth)acrylate rubber component as so entangled that they arenot separated from each other, and has a mean particle size of from 0.01to 1 μm or so. The composite rubber grafted copolymers are better thansingle rubber grafted copolymers, as their effect of improving theimpact resistance of resin moldings is higher than that of the latter,single rubber grafted copolymers. Commercial products of such compositerubber grafted copolymers are available, for example, Metablen S-2001from Mitsubishi Rayon.

The amount of the component (C), core/shell-type, grafted rubber-likeelastomer in the resin composition falls between 0.2 and 10 parts byweight, preferably between 0.5 and 5 parts by weight, relative to 100parts by weight of the component (A), polycarbonate-based resin therein.If the grafted rubber-like elastomer content of the resin composition issmaller than 0.2 parts by weight, the impact resistance of the resincomposition will be low; but if larger than 10 parts by weight, theflame retardancy, the heat resistance and the stiffness of the resincomposition will be low. In general, 10 parts by weight of the elastomeris enough for the resin composition. Containing such a relatively smallamount of the component (C), core/shell-type grafted rubber-likeelastomer combined with a relatively small amount of the component (B),functional group-having silicone compound, the advantages of thepolycarbonate resin composition of the invention are remarkable. If anyother graft copolymer is used in place of the core/shell-type, graftedrubber-like elastomer therein, the impact strength of the resincomposition could be improved in some degree but the flame retardancythereof could not reach the desired level.

The three components of the polycarbonate resin composition of theinvention well attain the object of the invention to improve themoldability (melt flowability), the impact resistance and the flameretardancy of the resin composition. If desired, however, any known meltdrip inhibitor may be added to the resin composition for furtherimproving the melt drip resistance of the composition in fire, forexample, in combustion tests for flame retardancy of resin.

(D) Polyfluoro-olefin Resin:

Polyfluoro-olefin resin (D) is preferred for the melt drip inhibitor.The polyfluoro-olefin resin is a polymer or copolymer having an ordinaryfluoroethylene structure. For example, it includes difluoroethylenepolymer, tetrafluoroethylene polymer,tetrafluoroethylene-hexafluoropropylene copolymer, and copolymer oftetrafluoroethylene with an ethylenic monomer not containing fluorine.Preferred is polytetrafluoroethylene (PTFE), and its mean molecularweight is preferably at least 500,000, more preferably from 500,000 to10,000,000. Any and every type of polytetrafluoroethylene known in theart is usable herein.

Polytetrafluoroethylene having the ability to form fibrils is morepreferred, as it ensures higher melt drip inhibition. The fibril-formingpolytetrafluoroethylene (PTFE) is not specifically defined, butpreferred is PTFE of Type 3 stipulated in the ASTM Standard. Specificexamples of PTFE of Type 3 include Teflon 6-J (from Mitsui-DuPontFluorochemical), Polyflon D-1, Polyflon F-103, Polyflon F201 (fromDaikin Industry), and CD076 (from Asahi ICI Fluoropolymers).

Others except PTFE of Type 3 are also employable herein, including, forexample, Argoflon F5 (from Montefluos), Polyflon MPA and Polyflon FA-100(from Daikin Industry). These polytetrafluoroethylenes (PTFE) may beused either singly or as combined. The fibril-formingpolytetrafluoroethylene (PTFE) as above may be obtained, for example, bypolymerizing tetrafluoroethylene in an aqueous solvent in the presenceof sodium, potassium or ammonium peroxydisulfide, under a pressurefalling between 0.01 and 1 MPa, at a temperature falling between 0 and200° C., preferably between 20 and 100° C.

The amount of the polyfluoro-olefin resin that may be in the resincomposition preferably falls between 0.02 and 5 parts by weight, morepreferably between 0.05 and 2 parts by weight relative to 100 parts byweight of the component (A), polycarbonate-based resin therein. If theamount therein is smaller than 0.02 parts by weight, the meltdrip-inhibiting ability of the composition will be not enough for theintended flame retardancy of the composition. However, even if itsamount is larger than 5 parts by weight, the effect of thepolyfluoro-olefin resin added could not be augmented any more, and sucha large amount of the polyfluoro-olefin resin, if added to thecomposition, will have some negative influences on the impact resistanceand the outward appearance of the moldings of the composition.Therefore, the amount of the polyfluoro-olefin resin to be added to thecomposition may be suitably determined, depending on the necessary flameretardancy of the moldings of the composition, for example, based onV-0, V-1 or V-2 in UL-94, and depending on the amount of the otherconstituent components of the composition.

The polycarbonate resin composition of the invention may contain, ifdesired, an inorganic filler which is for enhancing the stiffness of theresin moldings and for further enhancing the flame retardancy thereof.The inorganic filler includes, for example, talc, mica, kaolin,diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate,glass fibers, carbon fibers, and potassium titanate fibers. Especiallypreferred for use herein are tabular fillers of, for example, talc andmica, and fibrous fillers such as glass fibers and carbon fibers. Talcis a magnesium silicate hydrate, and this is available on the market.The inorganic filler such as talc for use herein may have a meanparticle size of from 0.1 to 50 μm, but preferably from 0.2 to 20 μm.The inorganic filler, especially talc in the resin composition iseffective for further enhancing the stiffness of the moldings of thecomposition, and, as the case may be, it will be able to reduce theamount of the silicone compound to be in the composition.

The amount of the inorganic filler content that may be in the resincomposition preferably falls between 1 and 100 parts by weight, morepreferably between 2 and 50 parts by weight relative to 100 parts byweight of the component (A), polycarbonate-based resin therein. If itsamount is smaller than 1 part by weight, the inorganic filler addedcould not satisfactorily exhibit its effect of enhancing the stiffnessand the flame retardancy of the resin composition; but if larger than100 parts by weight, the impact resistance and the melt flowability ofthe resin composition will lower. The amount of the inorganic filler tobe in the resin composition may be suitably determined, depending on thenecessary properties of the resin moldings and the moldability of thecomposition, especially on the thickness of the moldings and the spiralflow length of the composition.

The second aspect of the invention also provides a polycarbonate resincomposition, which comprises 100 parts by weight of a resin mixture offrom 1 to 99% by weight of a polycarbonate-based resin (A) that containsa polycarbonate resin terminated with a phenoxy group having an alkylgroup with from 21 to 35 carbon atoms, and from 1 to 99% by weight of astyrenic resin (E), and from 0.01 to 5 parts by weight of apolyfluoro-olefin resin (D).

The polycarbonate resin composition of the second aspect of theinvention is characterized in that its constituent component (A),polycarbonate-based resin contains a polycarbonate resin terminated witha phenoxy group having an alkyl group with from 21 to 35 carbon atoms(this will be hereinafter referred to as a terminal-modified PC). Inthis, the terminal-modified PC may be the same as that mentionedhereinabove to be in the component (A).

(E) Styrenic Resin:

For the styrenic resin for the constituent component (E) of thepolycarbonate resin composition of the second aspect of the invention,usable are polymers that are prepared through polymerization of amonomer or monomer mixture of from 20 to 100% by weight of a monovinylicaromatic monomer such as styrene or α-methylstyrene, from 0 to 60% byweight of a vinyl cyanide-type monomer such as acrylonitrile ormethacrylonitrile, and from 0 to 50% by weight of any other vinylicmonomer copolymerizable with those monomers, such as maleimide or methyl(meth)acrylate. The polymers include, for example, polystyrenes (GPPS),acrylonitrile-styrene copolymers (AS resins).

For the styrenic resin, also preferably used herein are rubber-modifiedstyrenic resins. The rubber-modified styrenic resins are preferablyhigh-impact styrenic resins that are produced through graftingpolymerization of rubber with at least styrenic monomers. Therubber-modified styrenic resins include, for example, high-impactpolystyrenes (HIPS) produced through polymerization of rubber such aspolybutadiene with styrene; ABS resins produced through polymerizationof polybutadiene with acrylonitrile and styrene; MBS resins producedthrough polymerization of polybutadiene with methyl methacrylate andstyrene. These rubber-modified styrenic resins may be combined, or maybe mixed with other styrenic resins not modified with rubber such asthose mentioned above, and the resin mixtures may be used in theinvention.

In the rubber-modified styrenic resins, the amount of rubber to modifythem may fall, for example, between 2 and 50% by weight, but preferablybetween 5 and 30% by weight, more preferably between 5 and 15% byweight. If the rubber content is smaller than 2% by weight, the impactresistance of the resin moldings will be poor. If, on the other hand, itis larger than 50% by weight, the thermal stability of the resincomposition will be lowered, and the melt flowability thereof will bealso lowered. If so, in addition, the resin composition will beunfavorably gelled or yellowed.

Specific examples of rubber for use herein include polybutadiene,acrylate and/or methacrylate-having rubber-like polymers,styrene-butadiene-styrene rubber (SBS), styrene-butadiene rubber (SBR),butadiene-acrylic rubber, isoprene rubber, isoprene-styrene rubber,isoprene-acrylic rubber, and ethylene-propylene rubber. Of those,especially preferred is polybutadiene. The polybutadiene usable hereinmay be any of low-cis polybutadiene (for example, having from 1 to 30mol % of 1,2-vinyl bonds and from 30 to 42 mol % of 1,4-cis bonds) orhigh-cis polybutadiene (for example, having at most 20 mol % of1,2-vinyl bonds and at least 78 mol % of 1,4-cis bonds), and even theirmixtures.

Containing the resin mixture of polycarbonate resin and styrenic resin,the melt flowability of the polycarbonate resin composition of theinvention is high. The blend ratio of the two resins to give the resinmixture is as follows: The amount of the component (A),polycarbonate-based resin is from 1 to 99% by weight, preferably from 50to 98% by weight, more preferably from 70 to 95% by weight; and that ofthe styrenic resin (E) is from 1 to 99% by weight, preferably from 2 to50% by weight, more preferably from 5 to 30% by weight. If the amount ofthe component (A), polycarbonate-based resin is smaller than 1% byweight, the heat resistance and the strength of the resin moldings willbe low; and if the amount of the component (E), styrenic resin issmaller than 1% by weight, the moldability of the resin composition willbe poor. For the styrenic resin (E), preferred are rubber-modifiedstyrenic resins such as those mentioned hereinabove. In case where therubber-modified polystyrene resin is used for the component (E), theblend ratio of the two resins is preferably as follows: The amount ofthe component (A), polycarbonate-based resin is from 70 to 98% byweight, and that of the rubber-modified polystyrene resin (E) is from 2to 30% by weight.

The resin blend ratio may be suitably determined, depending on theterminal-modified polycarbonate resin, the molecular weight of otherpolycarbonate resin, the type of styrenic resin, the melt flow rate ofthe resin composition, the rubber content of the resin composition, andon the use of the resin moldings, especially the size and the thicknessthereof.

(D) Polyfluoro-olefin Resin:

This may be the same as that for the component (D) mentionedhereinabove.

The amount of the polyfluoro-olefin resin in the resin composition isfrom 0.01 to 5 parts by weight, preferably from 0.05 to 2 parts byweight relative to 100 parts by weight of the resin mixture of thecomponents (A) and (E) therein.

If the amount of the polyfluoro-olefin resin therein is smaller than0.01 parts by weight, the melt drip-inhibiting ability of thecomposition will be not enough for the intended flame retardancy of thecomposition. However, even if its amount is larger than 5 parts byweight, the effect of the polyfluoro-olefin resin added could not beaugmented any more. Therefore, the amount of the polyfluoro-olefin resinto be added to the composition may be suitably determined, depending onthe necessary flame retardancy of the moldings of the composition, forexample, based on V-0, V-1 or V-2 in UL-94, and depending on the amountof the other constituent components of the composition.

(B) Functional Group-having Silicone Compound:

For further enhancing its flame retardancy, the resin compositionpreferably contains a functional group-having silicone compound, whichmay be the same as that mentioned hereinabove for the component (B).

The amount of the functional group-having silicone compound that may bein the resin composition is preferably from 0.1 to 10 parts by weight,more preferably from 0.2 to 5 parts by weight relative to 100 parts byweight of the resin mixture of the components (A) and (E) therein. Ifthe amount of the silicone compound therein is smaller than 0.1 parts byweight, the resin composition could not be resistant to flames; but evenif larger than 10 parts by weight, the silicone compound could no moreaugment its effect. In case where the polycarbonate-based resin in theresin composition contains PC-PDMS copolymer, the functionalgroup-having silicone compound content of the resin composition may besuitably determined in consideration of the overall silicone content ofthe resin composition. In that case, since the resin compositioncontains some silicone in addition to the functional group-havingsilicone compound, the functional group-having silicone compound contentof the resin composition may be reduced. Another advantage of the caseis that the level of the flame retardancy of the resin composition iskept high even when the overall silicone content of the resincomposition is lowered.

(F) Inorganic Filler:

The polycarbonate resin composition of the second aspect of theinvention may contain an inorganic filler for enhancing the stiffness ofthe resin moldings. The inorganic filler may be the same as thatmentioned hereinabove.

The amount of the inorganic filler that may be in the resin compositionis preferably from 1 to 100 parts by weight, more preferably from 2 to50 parts by weight relative to 100 parts by weight of the resin mixtureof the components (A) and (E) therein. If its amount is smaller than 1part by weight, the inorganic filler added could not satisfactorilyexhibit its effect of enhancing the stiffness and the flame retardancyof the resin composition; but if larger than 100 parts by weight, theimpact resistance and the melt flowability of the resin composition willlower. The amount of the inorganic filler to be in the resin compositionmay be suitably determined, depending on the necessary properties of theresin moldings and the moldability of the composition, especially on thethickness of the moldings and the spiral flow length of the composition.

In addition to the indispensable components (A), (B) and (C) and theoptional components (D) and inorganic filler, or in addition to theindispensable components (A), (E) and (D) and the optional components(B) and (F), the polycarbonate resin composition of the invention maycontain any other additives which are generally added to ordinarythermoplastic resins such as polyester resins and polyamide resins, ifdesired. The additives are for further improving the moldability of thecomposition and for further improving the impact resistance, the outwardappearances, the weather resistance and the stiffness of the moldings ofthe composition. They include, for example, phenolic,phosphorus-containing or sulfur-containing antioxidants, antistaticagents, polyamide-polyether block copolymers (for permanent staticelectrification resistance), benzotriazole-type or benzophenone-type UVabsorbents, hindered amine-type light stabilizers (weather-proofingagents), plasticizers, microbicides, compatibilizers, and colorants(dyes, pigments). The amount of the optional additives that may be inthe polycarbonate resin composition of the invention is preferably sodefined that they do not interfere with the properties of thecomposition.

Methods for producing the polycarbonate resin composition of theinvention are described. The resin composition may be produced by mixingand kneading the indispensable components and the optional components ina predetermined ratio as above. Formulating and mixing the constituentcomponents into the intended resin composition may be effected in anyknown manner, for example, by premixing them in an ordinary device, suchas a ribbon blender or a drum tumbler, followed by further kneading theresulting pre-mix in a Banbury mixer, a single-screw extruder, adouble-screw extruder, a multi-screw extruder or a cokneader. Thetemperature at which the components are mixed and kneaded generallyfalls between 240 and 300° C. For molding the melt mixture, preferablyused is an extrusion molding machine, more preferably a vented extruder.Other constituent components than polycarbonate resin may be previouslymixed with polycarbonate resin or with any other thermoplastic resin toprepare a master batch.

Having been prepared in the manner as above, the polycarbonate resincomposition of the invention may be molded into various moldings in themelt-molding devices as above, or, after it is pelletized, the resultingpellets may be molded into various moldings through injection molding,injection compression molding, extrusion molding, blow molding,pressing, vacuum forming or foaming. Especially preferably, thecomposition is pelletized in the melt-kneading manner as above, and theresulting pellets are molded into moldings through injection molding orinjection compression molding. For injection molding of the composition,employable is a gas-assisted molding method which is effective forpreventing the moldings from having sinking marks on their surfaces andfor reducing the weight of the moldings.

Moldings of the polycarbonate resin composition of the invention areusable for various housings and parts of electric and electronicappliances, such as copiers, facsimiles, televisions, radios, taperecorders, video decks, personal computers, printers, telephones,information terminals, refrigerators, and microwave ovens. The moldingshave still other applications, and are usable, for example, asautomobile parts.

The second aspect of the invention is described more concretely withreference to its Production Examples, Examples and Comparative Examples,which, however, are not intended to restrict the scope of the invention.

[Preparation of Alkylphenol]

Starting compounds, 300 parts by weight of phenol and 110 parts byweight of 1-docosene in a molar ratio of phenol/olefin=9/1, and 11 partsby weight of a catalyst, strong-acid polystyrenic sulfonate cation resin(Amberlyst 15 from Rohm and Haas) were put into a reactor equipped witha baffle and a stirring blade, and reacted at 120° C. with stirring for3 hours. After the reaction, the mixture was purified throughdistillation under reduced pressure to obtain an alkylphenol (a). In theresulting alkylphenol (a), the alkyl group had 22 carbon atoms.

[Production of PC Oligomer]

60 kg of bisphenol A was dissolved in 400 liters of aqueous 5 wt. %sodium hydroxide solution to prepare an aqueous solution of bisphenol Ain sodium hydroxide.

Next, the aqueous solution of bisphenol A in sodium hydroxide kept atroom temperature was fed into a tubular reactor having an inner diameterof 10 mm and a length of 10 m, at a flow rate of 138 liters/hr via anorifice plate of the reactor, along with methylene chloride thereintovia the plate at a flow rate of 69 liters/hr, while, at the same time,phosgene was also thereinto at a flow rate of 10.7 kg/hr, and they werecontinuously reacted for 3 hours. The tubular reactor used herein is ajacketed tube, in which cooling water was circulated through the jacketso as to keep the reaction mixture discharge at 25° C. The pH of thedischarge was controlled to fall between 10 and 11.

The thus-obtained reaction mixture was kept static for phase separation.Its aqueous phase was removed, and its methylene chloride phase (220liters) was collected to obtain a PC oligomer (concentration, 317g/liter). The degree of polymerization of the PC oligomer fell between 2and 4, and the chloroformate concentration thereof was 0.7 normalities.

[Production of Terminal-modified Polycarbonate]

10 liters of the PC oligomer obtained in above Production Example wasput into a 50-liter reactor equipped with a stirrer, and 247 g of thealkylphenol (a) was dissolved therein. Next, aqueous sodium hydroxidesolution (sodium hydroxide 53 g, water 1 liter) and 5.8 cc oftriethylamine were added thereto and reacted by stirring at 300 rpm for1 hour. Then, the system was mixed with a solution of bisphenol A insodium hydroxide (bisphenol A 720 g, sodium hydroxide 412 g, water 5.5liters), 8 liters of methylene chloride was added thereto, and thesewere reacted by stirring at 500 rpm for 1 hour. After the reaction, 7liters of methylene chloride and 5 liters of water were added to thesystem, and stirred at 500 rpm for 10 minutes. After stirring wasstopped, the system was kept static for phase separation into an organicphase and an aqueous phase. The resulting organic phase was washed with5 liters of an alkali (0.03-N NaOH), 5 liters of an acid (0.2-N HCl) and5 liters of water (twice) in that order. Next, methylene chloride wasevaporated away to obtain a flaky polymer. Its viscosity-averagemolecular weight was 17,500.

[Production of Reactive PDMS]

1483 g of octamethylcyclotetrasiloxane, 96 g of1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixedand stirred at room temperature for 17 hours. The resulting oily phasewas separated, and 25 g of sodium hydrogencarbonate was added theretoand stirred for 1 hour. After filtered, this was distilled in vacuum of3 Torr (4×10² Pa) at 150° C. to remove the low-boiling fraction, and theresidual oil was collected.

To a mixture of 60 g of 2-allylphenol and 0.0014 g of a platinumcompound, platinum chloride-alcoholate complex, added was 294 g of theoil at 90° c. While kept at 90 to 115° C., the resulting mixture wasstirred for 3 hours. The resulting product was extracted with methylenechloride and washed three times with aqueous 80% methanol to remove theexcess 2-allylphenol. This was dried with anhydrous sodium sulfate andthen heated in vacuum at 115° C. to remove the solvent.

Through its NMR, the thus-obtained, phenol-terminated PDMS was found tohave 30 repetitive dimethylsilanoxy units.

[Production of PC-PDMS Copolymer]

182 g of the reactive PDMS obtained in the above was dissolved in 2liters of methylene chloride, and this was mixed with 10 liters of thePC oligomer obtained in above Production Example. To this were added asolution of 26 g of sodium hydroxide in 1 liter of water and 5.7 cc oftriethylamine, and these were reacted by stirring at 500 rpm at roomtemperature for 1 hour.

To the resulting reaction system, added were a solution of 600 g ofbisphenol A dissolved in 5 liters of aqueous 5.2 wt. % sodium hydroxide,8 liters of methylene chloride, and 96 g of p-tert-butylphenol, andthese were reacted by stirring at 500 rpm at room temperature for 2hours.

5 liters of methylene chloride was added to the resulting reactionsystem, which was then washed with 5 liters of water, 5 liters of analkali, 0.03-N sodium hydroxide, 5 liters of an acid, 0.2-N hydrochloricacid, and 5 liters of water (two times) in that order. Finally,methylene chloride was removed from this, and a flaky PC-PDMS copolymerwas obtained. This was dried in vacuum at 120° C. for 24 hours. Itsviscosity-average molecular weight was 17,000, and its PDMS content was4.0% by weight.

The viscosity-average molecular weight and the PDMS content weremeasured as follows:

(1) Viscosity-average Molecular Weight (Mv):

The viscosity of the copolymer in methylene chloride at 20° C. wasmeasured with an Ubbelohde's viscometer, and the intrinsic viscosity [η]thereof was derived from it. The viscosity-average molecular weight (Mv)of the copolymer was calculated according to the following equation:[η]=1.23×10⁻⁵ Mv ^(0.83).(2) PDMS Content:

Based on the intensity ratio of the methyl peak of the isopropyl groupof bisphenol A seen at 1.7 ppm in ¹H-NMR of the copolymer to the methylpeak of the dimethylsiloxane moiety seen at 0.2 ppm therein, the PDMScontent of the copolymer was obtained.

[Production of Terminal-modified PC-PDMS Copolymer]

A terminal-modified PC-PDMS copolymer was produced in the same manner asin producing the PC-PDMS copolymer, for which, however, 257 g of thealkylphenol (a) was used in place of 96 g of p-tert-butylphenol. Thethus-obtained, terminal-modified PC-PDMS copolymer was dried in vacuumat 120° C. for 24 hours. Its viscosity-average molecular weight was17,000, and its PDMS content was 4.0% by weight.

EXAMPLES II-1 TO II-4, AND COMPARATIVE EXAMPLES II-1 TO II-7

The components shown in Table II-1 were blended in different ratios astherein [the amount of the component (A) is in terms of % by weight, andthat of the other components is in terms of parts by weight relative to100 parts by weight of the component (A)], fed into a venteddouble-screw extruder (TEM35 from Toshiba Kikai), melted and kneadedtherein at 280° C., and then pelletized. To all compositions of Examplesand Comparative Examples, added were 0.2 parts by weight of Irganox 1076(from Ciba Specialty Chemicals) and 0.1 parts by weight of Adekastab C(from Asahi Denka Industry) both serving as an antioxidant. Theresulting pellets were dried at 120° C. for 12 hours, and then moldedinto test pieces in a mode of injection molding at 270° C. The moldtemperature was 80° C. These test pieces were tested for theirproperties in various test methods, and their data obtained are given inTable II-1. In the Table, “Example II-1” is simply designated as“Example 1”, and the same shall apply to Comparative Examples.

The materials used for producing the test samples, and the methods fortesting the samples are mentioned below.

(A) Polycarbonate Resin:

-   PC-1: Toughlon A1700 (from Idemitsu Petrochemical).    -   This is a bisphenol A polycarbonate resin having a melt flow        rate (MFR) of 27 g/10 min (measured at 300° C. under a load of        11.77 N according to JIS K 7210) and a viscosity-average        molecular weight of 17,000, and terminated with        p-tert-butylphenoxy group.-   PC-2: Toughlon A1500 (from Idemitsu Petrochemical).    -   This is a bisphenol A polycarbonate resin having an MFR of 50        g/10 min and a viscosity-average molecular weight of 15,000, and        terminated with p-tert-butylphenoxy group.        Terminal-modified PC:    -   This is the p-docosylphenoxy-terminated polycarbonate resin        obtained in the above.-   PC-PDMS:    -   This is the bisphenol A-polydimethylsiloxane (PDMS) copolymer        obtained in the above, having a PDMS content of 4.0% by weight        and a viscosity-average molecular weight of 17,000, and        terminated with p-tert-butylphenoxy group.        (B) Silicone Compound:-   Silicone-1: KR219 (from Shin-etsu Chemical Industry).    -   This is methylphenylsilicone with vinyl and methoxy groups,        having a kinematic viscosity of 18 mm²/sec.-   Silicone-3: SH200 (from Toray Dow-Corning).    -   This is dimethylsilicone having a kinematic viscosity of        (C) Core/shell-type, Grafted Rubber-like Elastomer:        Rubber-Like Elastomer-1: Metablen S2001 (from Mitsubishi Rayon).    -   This is a composite rubber-like graft copolymer having a        polydimethylsiloxane content of at least 50% by weight.-   Rubber-Like Elastomer-2: VECTOR 8550-5 (from Dexco Polymers).    -   This is an SBS-type graft copolymer (for comparison).        (D) Polyfluoro-olefin Resin:    -   PTFE: CD076 (from Asahi ICI Fluoropolymers).        [Test Methods]        (1) Melt Flowability:

MFR (melt flow rate) of each sample is measured at 300° C. under a loadof 11.77 N, according to JIS K 7210.

(2) IZOD Impact Strength:

Measured according to ASTM D256 at 23° C. The samples are 3.2 mm thick.

(3) Flame Retardancy:

Tested according to the combustion test of UL94. V-2NG indicates thatthe samples tested do not correspond to any of V-0, V-1 and V-2.

(4) Grease Resistance:

Measured according to a chemical resistance test method (for measuringthe critical deflection of a test sample on a quarter oval tool).

on a quarter oval tool).

Concretely, a test sample (having a thickness of 3 mm) is fixed on aquarter oval tool as in FIG. II-1 (showing a perspective view of thetool), Albanian grease (from Showa Shell Petroleum) is applied thereto,and this is kept as such for 48 hours. The shortest length (X) of thetool on which the sample has been cracked is read, and the criticaldeflection (%) of the sample is obtained according to the followingequation (II-1).Critical Deflection (%)=b/2a ²×[1−(1/a ² −b ² /a ⁴)X ²]^(−3/2)·t×100  (II-1),

-   -   in which t indicates the thickness of the test sample.        (5) Recyclability:

Resin composition pellets are molded in a mode of injection molding at300° C. into housings for notebook-size personal computers (of A4 size).The mold temperature is 80° C. The housings are ground, and 100%recycled into test pieces molded in the same manner as previously.

The IZOD impact strength of the recycled test pieces is measured.

The color change of the recycled test pieces is measured. Concretely,the color (L, a, b) of the original test pieces and that of the recycledtest pieces are measured with a calorimeter, according to JIS H 7103(test method for yellowing). From the data, obtained is the colordifference, ΔE between the original test pieces and the recycled testpieces.

TABLE II-1-(1) Example 1 Example 2 Example 3 Example 4 Co. Ex. 1 Co. Ex.2 Composition (A) PC-1: A1700 25 100 PC-2: A1500 Terminal-modified PC100 100 75 50 100 PC-PDMS 25 25 PDMS content of resin (A) 0 0 1.0 1.0 00 (wt. %) (B) Silicone-1 3 3 1 1 3 Silicone-3 (for comparison) (C)Rubber-like elastomer-1 1 1 2 2 1 1 Rubber-like elastomer-2 (forcomparison) (D) PTFE 0.5 0.3 0.3 0.5 Evaluation (1) Melt flowability:MFR (g/10 min) 45 45 47 44 28 43 (2) IZOD impact strength (kJ/m²) 60 6055 65 65 60 (3) Flame test piece 1.5 mm V-2 V-0 V-0 V-0 V-2NG V-2NGretardancy 94 thick UL-94 test piece 2.5 mm V-2 V-0 V-0 V-0 V-2 V-2NGthick (4) Grease resistance 1.0 1.0 0.9 0.8 0.8 1.0 (5) RecyclabilityIZOD impact 60 60 50 60 60 60 strength (kJ/m²) color change (ΔE) 1.3 1.41.2 1.4 1.5 1.3

TABLE II-1-(2) Co. Ex. 3 Co. Ex. 4 Co. Ex. 5 Co. Ex. 6 Co. Ex. 7Composition (A) PC-1: A1700 50 100 PC-2: A1500 50 Terminal-modified PC100 75 75 PC-PDMS 25 25 PDMS content of resin (A) 0 0 0 1.0 1.0 (wt. %)(B) Silicone-1 3 3 3 1 Silicone-3 (for comparison) 1 (C) Rubber-likeelastomer-1 1 1 2 Rubber-like elastomer-2 (for 2 comparison) (D) PTFE0.5 0.5 0.5 0.3 0.3 Evaluation (1) Melt flowability: MFR (g/10 min) 4536 28 46 46 (2) IZOD impact strength (kJ/m²) 15 20 65 55 60 (3) Flametest piece 1.5 mm V-0 V-0 V-0 V-2NG V-2NG retardancy 94 thick UL-94 testpiece 2.5 mm V-0 V-0 V-0 V-2NG V-2NG thick (4) Grease resistance 0.8 0.40.8 0.7 0.7 (5) Recyclability IZOD impact 10 10 65 40 55 strength(kJ/m²) color change (ΔE) 1.4 1.2 1.2 3.5 1.4

EXAMPLES II-5 TO II-11, AND COMPARATIVE EXAMPLES II-8 TO II-13

The components shown in Table II-2 were blended in different ratios astherein [the amount of the component (A) and the component (E) is interms of % by weight, and that of the other components is in terms ofparts by weight relative to 100 parts by weight of the resin mixture ofthe components (A) and (E)], fed into a vented double-screw extruder(TEM35 from Toshiba Kikai), melted and kneaded therein at 280° C., andthen pelletized. To all compositions of Examples and ComparativeExamples, added were 0.2 parts by weight of Irganox 1076 (from CibaSpecialty Chemicals) and 0.1 parts by weight of Adekastab C (from AsahiDenka Industry) both serving as an antioxidant. The resulting pelletswere dried at 120° C. for 12 hours, and then molded into test pieces ina mode of injection molding at 270° C. The mold temperature was 80° C.These test pieces were tested for their properties in various testmethods, and their data obtained are given in Table II-2. In the Table,“Example II-5” is simply designated as “Example 5”, and the same shallapply to Comparative Examples.

The materials used for producing the test samples, and the methods fortesting the samples are mentioned below.

(A) Polycarbonate Resin:

-   PC-2: Same as above.-   PC-3: Toughlon A1900 (from Idemitsu Petrochemical).    -   This is a bisphenol A polycarbonate resin having an MFR of 19        g/10 min (measured at 300° C. under a load of 11.77 N according        to JIS K 7210) and a viscosity-average molecular weight of        19,000, and terminated with p-tert-butylphenoxy group.        Terminal-modified PC: Same as above.-   PC-PDMS: Same as above.    Terminal-modified PC-PDMS:    -   This is the bisphenol A-polydimethylsiloxane (PDMS) copolymer        obtained in the above, having a PDMS content of 4.0% by weight        and a viscosity-average molecular weight of 17,100, and        terminated with p-docosylphenoxy group.        (E) Styrenic Resin:-   HIPS (High-impact Polystyrene): IDEMITSU PS IT44 (from Idemitsu    Petrochemical).    -   This is a polybutadiene-styrene graft copolymer, having a rubber        content of 10% by weight and MFR of 8 g/10 min (measured at        200° C. under a load of 49.03 N according to JIS K 7210).-   ABS (Acrylonitrile-butadiene-styrene Copolymer): DP-611 (from    Technopolymer), Having MFR of 2 g/10 min.    (D) Polyfluoro-Olefin Resin:-   PTFE: Same as above.-   (B) Silicone Compound:-   Silicone-1: Same as above.    Silicone-2: KC-89 (from Shin-etsu Chemical Industry).    -   This is methoxy group-having dimethylsilicone, having a        kinematic viscosity of 20 mm²/sec.        (F) Inorganic Filler:-   Talc: FFR (from Asada Milling), having a mean particle size of 0.7    μm.

The test methods are the same as those mentioned hereinabove.

TABLE II-2-(1) Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Composition(A) PC-1: A1500 PC-3: A1900 Terminal-modified PC 90 90 80 65 90 10 50PC-PDMS 25 80 Terminal-modified PC-PDMS 40 PDMS content of resin (A) 0 00 1.0 0 3.2 1.6 (wt. %) (E) HIPS 10 10 10 10 10 10 ABS 20 (D) PTFE 0.50.5 0.3 0.5 0.5 0.5 0.5 (B) Silicone-1 4 4 4 Silicone-2 2 (F) Talc 10 5010 Evaluation (1) Melt flowability MFR (g/10 min) 16 20 24 14 17 8 18(2) IZOD impact strength (kJ/m²) 60 60 65 75 45 55 60 (3) Flame testpiece 1.5 V-2NG V-2NG V-2NG V-2NG V-0 V-0 V-0 retardancy 94 mm thickUL-94 test piece 2.5 V-2NG V-0 V-1 V-0 V-0, 5VB V-0, 5VB V-0, 5VB mmthick (4) Grease resistance 1.2 1.2 1.5 1.2 1.5 1.3 1.3 (5)Recyclability Izod impact 55 50 55 70 35 45 50 strength (kJ/m²) colorchange (ΔE) 1.5 1.3 2.2 1.4 2.0 3.0 1.8 Co. Ex. 8 Co. Ex. 9 Co. Ex. 10Co. Ex. 11 Co. Ex. 12 Co. Ex. 13 Composition (A) PC-1: A1500 45 PC-3:A1900 90 90 45 90 Terminal-modified PC 100 90 PC-PDMS Terminal-modifiedPC-PDMS PDMS content of resin (A) 0 0 0 0 0 0 (wt. %) (E) HIPS 10 10 1010 10 ABS (D) PTFE 0.5 0.5 0.5 0.5 0.5 (B) Silicone-1 4 4 4 4 4Silicone-2 (F) Talc 10 Evaluation (1) Melt flowability: MFR (g/10 min) 68 12 6 3 20 (2) IZOD impact strength (kJ/m²) 60 65 20 40 10 60 (3) Flametest piece 1.5 V-2NG V-2NG V-2NG V-0 V-0 V-2NG retardancy 94 mm thickUL-94 test piece 2.5 V-2NG V-0 V-0 V-0, 5VB V-0, 5VB V-2NG mm thick (4)Grease resistance 1.2 1.2 0.6 1.0 0.4 1.2 (5) Recyclability IZOD impact55 60 10 35 3 50 strength (kJ/m²) color change (ΔE) 1.5 1.4 1.5 3.1 1.41.4

From the data in Tables II-1 and II-2, it is obvious that themoldability (melt flowability) of the polycarbonate resin composition ofthe invention is good and the moldings of the composition have highimpact strength. In addition, the resin moldings are resistant to greaseand are recyclable.

[III] Third Aspect of the Invention:

The component (A) of the resin composition of the third aspect of theinvention (in this section, the “third aspect of the invention” will besimply referred to as “the invention”) is an aromaticpolycarbonate-polyorganosiloxane copolymer having a terminal group offormula (III-1) mentioned above (this is hereinafter abbreviated asPC-PDMS copolymer). For example, it includes copolymers disclosed inJapanese Patent Laid-Open Nos. 29695/1975, 292359/1991, 202465/1992,81620/1996, 302178/1996 and 7897/1998. For it, preferred are copolymershaving an aromatic polycarbonate moiety of structural units of thefollowing structural formula (III-3) and a polyorganosiloxane moiety ofstructural units of the following structural formula (III-4) in themolecule.

In these, R³ and R⁴ each represent an alkyl group having from 1 to 6carbon atoms, or a phenyl group, and they may be the same or different.R⁵ to R⁸ each represent an alkyl group having from 1 to 6 carbon atoms,or a phenyl group, preferably a methyl group. R⁵ to R⁸ may be the sameor different.

R⁹ represents an aliphatic or aromatic organic residue, preferably ano-allylphenol residue, a p-hydroxystyrene residue or a eugenol residue.

Z represents a single bond, an alkylene group having from 1 to 20 carbonatoms, an alkylidene group having from 1 to 20 carbon atoms, acycloalkylene group having from 5 to 20 carbon atoms, or acycloalkylidene group having from 5 to 20 carbon atoms, or a bond of—SO₂—, —SO—, —S—, —O— or —CO—. Preferably, it is an isopropylidenegroup.

b and c each indicate an integer of from 0 to 4, preferably 0. nindicates an integer of from 1 to 500, preferably from 5 to 100.

The PC-PDMS copolymer may be produced, for example, by dissolving apreviously-prepared aromatic polycarbonate oligomer (hereinafterabbreviated as PC oligomer), which is to form the aromatic polycarbonatemoiety of the copolymer, and a previously-prepared polyorganosiloxaneterminated with a reactive group such as an o-allylphenol,p-hydroxystyrene or eugenol residue (reactive PDMS), which is to formthe polyorganosiloxane moiety of the copolymer, in a solvent such asmethylene chloride, chlorobenzene or chloroform, then adding thereto anaqueous alkali hydroxide solution of a diphenol, and reacting them in amode of interfacial polycondensation in the presence of a tertiary amine(e.g., triethylamine) or a quaternary ammonium salt (e.g.,trimethylbenzylammonium chloride) serving as a catalyst and in thepresence of an ordinary terminal stopper of a phenol compound of thefollowing general formula (III-5):

wherein R¹ and a have the same meanings as above.

Concretely, for example, the terminal stopper includes phenol, p-cresol,p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol,p-tert-amylphenol, bromophenol, tribromophenol, pentabromophenol. Forit, preferred are non-halogen compounds for protecting the environment.

The PC oligomer to be used in producing the PC-PDMS copolymer is readilyprepared, for example, by reacting a diphenol of the following generalformula (III-6):

wherein R³, R⁴, Z, b and c have the same meanings as above, with acarbonate precursor such as phosgene or a carbonate compound, in asolvent such as methylene chloride.

Concretely, for example, it may be prepared through reaction of adiphenol with a carbonate precursor such as phosgene or throughinteresterification of a carbonate precursor such as diphenyl carbonatewith a diphenol, in a solvent such as methylene chloride.

The diphenol of formula (III-6) includes, for example,4,4′-dihydroxydiphenyl; bis(4-hydroxyphenyl)alkanes such as1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane; bis(4-hydroxyphenyl) oxide;bis(4-hydroxyphenyl) sulfide; bis(4-hydroxyphenyl) sulfone;bis(4-hydroxyphenyl) sulfoxide; bis(4-hydroxyphenyl) ether; andbis(4-hydroxyphenyl) ketone. Of those, preferred is2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Singly or as combined,one or more of these diphenols may be used for the reaction.

The carbonate compound includes, for example, diaryl carbonates such asdiphenyl carbonate; and dialkyl carbonates such as dimethyl carbonate,diethyl carbonate.

In the invention, the PC oligomer for use in producing the PC-PDMScopolymer may be a homopolymer or copolymer with one or more diphenolsmentioned above. In addition, it may also be a thermoplastic randombranched polycarbonate prepared by combining the diphenol with apolyfunctional aromatic compound. For it, the branching agent(polyfunctional aromatic compound) includes, for example,1,1,1-tris(4-hydroxyphenyl)ethane,α,α′α″-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene,1-[α-methyl-α-(4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis(4″-hydroxyphenyl)ethyl]benzene,phloroglucine, trimellitic acid, isatin-bis(o-cresol).

The component (A) may be produced in the manner as above, but ingeneral, it contains a by-product of aromatic polycarbonate.Accordingly, the component (A) produced in the manner as above is anaromatic polycarbonate resin that contains PC-PDMS copolymer, and itsviscosity-average molecular weight preferably falls between 10,000 and40,000 as a whole, more preferably between 12,000 and 30,000. Alsopreferably, the polyorganosiloxane content of the component (A) is from0.5 to 10% by weight of the total polycarbonate resin that contains thecomponent (A).

The polymer produced according to the method mentioned above isterminated by the group of formula (III-1) substantially at one or bothends of the molecule.

The component (B) of the resin composition of the invention is anaromatic polycarbonate having a terminal group of formula (III-2)mentioned above (this is hereinafter abbreviated as terminal-modifiedpolycarbonate), and its viscosity-average molecular weight preferablyfalls between 10,000 and 40,000, more preferably between 12,000 and30,000.

In formula (III-2), R² is an alkyl group having from 21 to 35 carbonatoms, and it may be linear or branched.

In this, the alkyl group may be at any of p-, m- or opposition, but ispreferably at p-position.

The terminal-modified polycarbonate may be readily prepared by reactinga diphenol with phosgene or a carbonate compound.

Concretely, for example, it is prepared through reaction of a diphenolwith a carbonate precursor such as phosgene or throughinteresterification of a carbonate precursor such as diphenyl carbonatewith a diphenol, in a solvent such as methylene chloride in the presenceof a catalyst such as triethylamine and a specific terminal stopper.

The diphenol may be the same as the compound of formula (III-6), or maydiffer from it. The terminal-modified polycarbonate may be a homopolymeror copolymer with one or more diphenols mentioned above. In addition, itmay also be a thermoplastic random branched polycarbonate prepared bycombining the diphenol with a polyfunctional aromatic compound.

Examples of the carbonate compound are diaryl carbonates such asdiphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate,diethyl carbonate.

For the terminal stopper, used are phenol compounds capable of forming aterminal group of formula (III-2). For example, used are phenolcompounds of the following general formula (III-7) in which R² has thesame meaning as above.

Examples of such alkylphenols are docosylphenol, tetracosylphenol,hexacosylphenol, octacosylphenol, triacontylphenol, dotriacontylphenoland tetratriacontylphenol. Singly or as combined, one or more of thesealkylphenols may be used herein. Not interfering with the effect of theinvention, the alkylphenol may be combined with any other phenol such asan alkylphenol having at most 20 carbon atoms.

The aromatic polycarbonate produced according to the method mentionedabove is terminated by the group of formula (III-2) substantially at oneor both ends of the molecule.

The aromatic polycarbonate resin containing the components (A) and (B)is prepared by mixing the aromatic polycarbonate resin containing thecomponent (A) with the component (B). If desired, it may contain anyother ordinary aromatic polycarbonate resin. Preferably, however, theviscosity-average molecular weight of the additional aromaticpolycarbonate resin falls between 10,000 and 40,000, more preferablybetween 12,000 and 30,000. The aromatic polycarbonate resin may beprepared in the same manner as that for preparing the component (B),using, as the terminal stopper, the ordinary phenol compound of formula(III-5). The diphenol for it may be the same as or different from thediphenol of formula (III-6) to be used in producing the component (A) aswell as the diphenol used in producing the component (B).

Preferably, the viscosity-average molecular weight of the total aromaticpolycarbonate resin that contains the components (A) and (B) fallsbetween 10,000 and 40,000, more preferably between 12,000 and 30,000,even more preferably between 14,000 and 26,000. If its molecular weightis too low, the mechanical strength of the resin composition of theinvention will be low; but if too high, the flowability of the resincomposition of the invention will be poor.

The polyorganosiloxane content of the component (A) preferably fallsbetween 0.1 and 2% by weight of the total aromatic polycarbonate resinthat contains the components (A) and (B) for better flame retardancy ofthe resin composition of the invention. More preferably, it fallsbetween 0.2 and 1.5% by weight, even more preferably between 0.5 and1.3% by weight.

Also preferably, the amount of the component (B), polycarbonate is atleast 10% by weight of the total aromatic polycarbonate resin thatcontains the components (A) and (B), more preferably between 30 and 90%by weight, even more preferably between 40 and 80% by weight. If theamount of the component (B) is smaller than 10% by weight, theflowability of the composition of the invention could not be increased.

The component (C), fibril-forming polytetrafluoroethylene having a meanmolecular weight of at least 500,000 (hereinafter this is abbreviated asPTFE) to be in the resin composition of the invention is for enhancingthe ability of the resin composition not to drip in melt, and ittherefore enhances the flame retardancy of the composition. Its meanmolecular weight must be at least 500,000, and is preferably from500,000 to 10,000,000, more preferably from 1,000,000 to 10,000,000.

The amount of the component (C) in the resin composition is from 0.05 to1 part by weight, preferably from 0.1 to 0.5 parts by weight relative to100 parts by weight of the aromatic polycarbonate resin therein thatcontains the components (A) and (B). If the amount is larger than 1 partby weight, it is unfavorable since too much PTFE will have negativeinfluences on the impact resistance and the appearance of the resinmoldings and, in addition, the resin strands containing too much PTFEwill meander when the resin composition is kneaded and extruded out, andif so, it is impossible to stably produce resin pellets. On the otherhand, if its amount is smaller than 0.05 parts by weight, the component(C) will be ineffective for melt drip inhibition. Within the preferredrange, the component (C) is more effective for melt drip inhibition andenhances the flame retardancy of the resin composition.

The fibril-forming PTFE for the component (C) is not specificallydefined, including, for example, Teflon 6-J (trade name fromMitsui-DuPont Fluorochemical), Polyflon D-1 and Polyflon F-103 (tradenames from Daikin Industry), Argoflon F5 (trade name from Montefluos),Polyflon MPA, FA-100 (trade names from Daikin Industry). Thesepolytetrafluoroethylenes (PTFE) may be used either singly or ascombined.

The fibril-forming polytetrafluoroethylene (PTFE) as above may beobtained, for example, by polymerizing tetrafluoroethylene in an aqueoussolvent in the presence of sodium, potassium or ammoniumperoxydisulfide, under a pressure falling between 7 and 700 kPa, at atemperature falling between 0 and 200° C., preferably between 20 and100° C.

The component (D) of the resin composition of the invention is anaromatic polycarbonate-polyorganosiloxane copolymer having a terminalgroup of formula (III-2′) mentioned above (this is hereinafterabbreviated as terminal-modified PC-PDMS copolymer).

In formula (III-2′), R²′ is an alkyl group having from 21 to 35 carbonatoms, which is the same as R² mentioned above.

The terminal-modified PC-PDMS copolymer is a copolymer that comprises anaromatic polycarbonate moiety and a polysiloxane moiety, and itsskeleton except the terminal group is the same as that of PC-PDMS in thefirst aspect of the invention. For it, preferred are copolymers havingan aromatic polycarbonate moiety of structural units of theabove-mentioned structural formula (III-3) and a polyorganosiloxanemoiety of structural units of the above-mentioned structural formula(III-4) in the molecule.

Like the PC-PDMS copolymer mentioned above, the terminal-modifiedPC-PDMS copolymer may be produced, for example, by dissolving apreviously-prepared aromatic polycarbonate oligomer (hereinafterabbreviated as PC oligomer), which is to form the aromatic polycarbonatemoiety of the copolymer, and a previously-prepared polyorganosiloxaneterminated with a reactive group such as an o-allylphenol,p-hydroxystyrene or eugenol residue (reactive PDMS), which is to formthe polyorganosiloxane moiety of the copolymer, in a solvent such asmethylene chloride, chlorobenzene or chloroform, then adding thereto anaqueous alkali hydroxide solution of a diphenol, and reacting them in amode of interfacial polycondensation in the presence of a tertiary amine(e.g., triethylamine) or a quaternary ammonium salt (e.g.,trimethylbenzylammonium chloride) serving as a catalyst and in thepresence of a terminal stopper of a phenol compound of the followinggeneral formula (III-7′):

wherein R²′ has the same meaning as above.

In formula (III-7′), R²′ has the same meaning as R² mentioned above.

The PC oligomer to be used in producing the terminal-modified PC-PDMScopolymer is readily prepared, for example, by reacting a diphenol offormula (III-6) with a carbonate precursor such as phosgene or acarbonate compound in a solvent such as methylene chloride.

Concretely, for example, it may be prepared through reaction of adiphenol with a carbonate precursor such as phosgene or throughinteresterification of a carbonate precursor such as diphenyl carbonatewith a diphenol, in a solvent such as methylene chloride.

The carbonate compound includes, for example, diaryl carbonates such asdiphenyl carbonate; and dialkyl carbonates such as dimethyl carbonate,diethyl carbonate.

In the invention, the PC oligomer for use in producing theterminal-modified PC-PDMS copolymer may be a homopolymer or copolymerwith one or more diphenols mentioned above. In addition, it may also bea thermoplastic random branched polycarbonate prepared by combining thediphenol with a polyfunctional aromatic compound. For it, the branchingagent (polyfunctional aromatic compound) includes, for example,1,1,1-tris(4-hydroxyphenyl)ethane,α,α′α″-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene,1-[α-methyl-α-(4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis(4′-hydroxyphenyl)ethyl]benzene,phloroglucine, trimellitic acid, isatin-bis(o-cresol).

The component (D) may be produced in the manner as above, but ingeneral, it contains a by-product of aromatic polycarbonate having aterminal group of formula (III-2′) (this is hereinafter abbreviated asterminal-modified polycarbonate). Accordingly, the component (D)produced in the manner as above is an aromatic polycarbonate resin thatcontains the terminal-modified PC-PDMS copolymer, and itsviscosity-average molecular weight preferably falls between 10,000 and40,000 as a whole, more preferably between 12,000 and 30,000.

Also preferably, the polyorganosiloxane content of the component (D) isfrom 0.5 to 10% by weight of the total aromatic polycarbonate resin thatcontains the component (D).

The polymer produced according to the method mentioned above isterminated by the group of formula (III-2′) substantially at one or bothends of the molecule.

In the invention, the aromatic polycarbonate resin containing thecomponent (D), which is produced according to the method mentionedabove, may be directly used as it is. If desired, however, it may becombined with any other ordinary aromatic polycarbonate resin or anadditional terminal-modified aromatic polycarbonate resin producedseparately from it. In that case, the sum of the amount of theterminal-modified PC-PDMS copolymer for the component (D) and the amountof the terminal-modified polycarbonate is preferably at least 10% byweight of the total aromatic polycarbonate resin that contains thecomponent (D), more preferably at least 30% by weight, even morepreferably at least 50% by weight. If it is smaller than 10% by weight,the flowability of the composition of the invention could not beimproved. Also preferably, the additional aromatic polycarbonate resinhas a viscosity-average molecular weight of from 10,000 to 40,000, morepreferably from 12,000 to 30,000.

The aromatic polycarbonate resin is not specifically defined, and may bereadily produced by reacting a diphenol with phosgene or a carbonatecompound.

Concretely, for example, it may be produced by reacting a diphenol witha carbonate precursor such as phosgene or by interesterifying acarbonate precursor such as diphenyl carbonate with a diphenol, in asolvent such as methylene chloride in the presence of a catalyst such astriethylamine and a terminal stopper.

The diphenol may be the same as or different from the compound offormula (III-6) used in producing the component (D). The polycarbonatemay be a homopolymer for which one and the same diphenol is used, or acopolymer for which two or more different types of diphenols are used.Further, it may also be a thermoplastic random-branched polycarbonatefor which the diphenol is combined with a polyfunctional aromaticcompound.

Examples of the dicarbonate compound are diaryl carbonates such asdiphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate ordiethyl carbonate.

The terminal stopper for ordinary aromatic polycarbonate resin includes,for example, phenol, p-tert-butylphenol, p-tert-octylphenol,p-cumylphenol, p-nonylphenol, p-tert-amylphenol, bromophenol,tribromophenol, pentabromophenol. For the terminal-modified aromaticpolycarbonate resin, the phenol compound of formula (III-7′) is used forthe terminal stopper.

Preferably, the viscosity-average molecular weight of the total aromaticpolycarbonate resin that contains the component (D) falls between 10,000and 40,000, more preferably between 12,000 and 30,000, even morepreferably between 14,000 and 26,000. If its molecular weight is toolow, the mechanical strength of the resin composition of the inventionwill be low; but if too high, the flowability of the resin compositionof the invention will be poor.

The polyorganosiloxane content of the component (D) preferably fallsbetween 0.1 and 2% by weight of the total aromatic polycarbonate resinthat contains the component (D) for better flame retardancy of the resincomposition of the invention. More preferably, it falls between 0.2 and1.5% by weight, even more preferably between 0.5 and 1.3% by weight.

The component (C), fibril-forming polytetrafluoroethylene having a meanmolecular weight of at least 500,000 (hereinafter this is abbreviated asPTFE) to be in the resin composition of the invention is for enhancingthe ability of the resin composition not to drip in melt, and ittherefore enhances the flame retardancy of the composition. Its meanmolecular weight must be at least 500,000, and is preferably from500,000 to 10,000,000, more preferably from 1,000,000 to 10,000,000.

The amount of the component (C) in the resin composition is from 0.05 to1 part by weight, preferably from 0.1 to 0.5 parts by weight relative to100 parts by weight of the aromatic polycarbonate resin therein thatcontains the component (D). If the amount is larger than 1 part byweight, it is unfavorable since too much PTFE will have negativeinfluences on the impact resistance and the appearance of the resinmoldings and, in addition, the resin strands containing too much PTFEwill meander when the resin composition is kneaded and extruded out, andif so, it is impossible to stably produce resin pellets. On the otherhand, if its amount is smaller than 0.05 parts by weight, the component(C) will be ineffective for melt drip inhibition. Within the preferredrange, the component (C) is more effective for melt drip inhibition andenhances the flame retardancy of the resin composition.

The fibril-forming PTFE for the component (C) is not specificallydefined, including those mentioned hereinabove for the first aspect ofthe invention, and it may be produced in the same manner as hereinabove.

Further if desired, the resin composition of the invention may containvarious types of inorganic fillers, additives, other synthetic resinsand elastomers not interfering with the object of the invention [theseare hereinafter abbreviated as component (E)].

The inorganic filler may be in the polycarbonate resin composition forenhancing the mechanical strength and the durability of the compositionand for increasing the amount of the composition. It includes, forexample, glass fibers (GF), carbon fibers, glass beads, glass flakes,carbon black, calcium sulfate, calcium carbonate, calcium silicate,titanium oxide, alumina, silica, asbestos, talc, clay, mica, quartzpowder. The additives are, for example, antioxidants such as hinderedphenol compounds, phosphorus-containing compounds (e.g., phosphites,phosphates), amine compounds; UV absorbents such as benzotriazolecompounds, benzophenone compounds; lubricants such as aliphaticcarboxylates, paraffin, silicone oil, polyethylene wax; mold releaseagents, antistatic agents and colorants.

Additional synthetic resins that may be in the resin composition of theinvention are, for example, polyethylene, polypropylene, polystyrene, ASresin (acrylonitrile-styrene copolymer), ABS resin(acrylonitrile-butadiene-styrene copolymer), and polymethylmethacrylate. The elastomers are, for example, isobutylene-isoprenerubber, styrene-butadiene rubber, ethylene-propylene rubber, and acrylicelastomers.

The resin composition of the invention may be produced by mixing andkneading the above-mentioned components optionally with (E).

Formulating and mixing the constituent components into the intendedresin composition may be effected in any known manner, for example,using a ribbon blender, a drum tumbler, a Henschel mixer, a Banburymixer, a single-screw extruder, a double-screw extruder, a cokneader ora multi-screw extruder. The temperature at which the components aremixed and kneaded generally falls between 240 and 320° C.

Having been prepared in the manner as above, the polycarbonate resincomposition of the invention may be molded in various molding methodsof, for example, injection molding, blow molding, extrusion molding,compression molding, calendering, spin molding. The resulting moldingsare favorable to housings and parts of electric and electronicappliances that are required to be resistant to flames.

The invention is described more concretely with reference to itsProduction Examples, Examples and Comparative Examples, which, however,are not intended to restrict the scope of the invention.

PRODUCTION EXAMPLE III-1

[Preparation of Alkylphenol (a)]

Starting compounds, 300 parts by weight of phenol and 110 parts byweight of 1-docosene in a molar ratio of phenol/olefin=9/1, and 11 partsby weight of a catalyst, strong-acid polystyrenic sulfonate cation resin(Amberlyst 15 from Rohm and Haas) were put into a reactor equipped witha baffle and a stirring blade, and reacted at 120° C. with stirring for3 hours. After the reaction, the mixture was purified throughdistillation under reduced pressure to obtain an alkylphenol (a). In theresulting alkylphenol (a), the alkyl group had 22 carbon atoms.

PRODUCTION EXAMPLE III-2

[Production of PC Oligomer]

60 kg of bisphenol A was dissolved in 400 liters of aqueous 5 wt. %sodium hydroxide solution to prepare an aqueous solution of bisphenol Ain sodium hydroxide.

Next, the aqueous solution of bisphenol A in sodium hydroxide kept atroom temperature was fed into a tubular reactor having an inner diameterof 10 mm and a length of 10 m, at a flow rate of 138 liters/hr via anorifice plate of the reactor, along with methylene chloride thereintovia the plate at a flow rate of 69 liters/hr, while, at the same time,phosgene was also thereinto at a flow rate of 10.7 kg/hr, and they werecontinuously reacted for 3 hours. The tubular reactor used herein is ajacketed tube, in which cooling water was circulated through the jacketso as to keep the reaction mixture discharge at 25° C. The pH of thedischarge was controlled to fall between 10 and 11.

The thus-obtained reaction mixture was kept static for phase separation.Its aqueous phase was removed, and its methylene chloride phase (220liters) was collected to obtain a PC oligomer (concentration, 317g/liter). The degree of polymerization of the PC oligomer fell between 2and 4, and the chloroformate concentration thereof was 0.7 normalities.

PRODUCTION EXAMPLE III-3-1

[Production of Reactive PDMS-A]

1483 g of octamethylcyclotetrasiloxane, 96 g of1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixedand stirred at room temperature for 17 hours. The resulting oily phasewas separated, and 25 g of sodium hydrogencarbonate was added theretoand stirred for 1 hour. After filtered, this was distilled in vacuum of3 Torr (4×10² Pa) at 150° C. to remove the low-boiling fraction, and theresidual oil was collected.

To a mixture of 60 g of 2-allylphenol and 0.0014 g of a platinumcompound, platinum chloride-alcoholate complex, added was 294 g of theoil at 90° c. While kept at 90 to 115° C., the resulting mixture wasstirred for 3 hours. The resulting product was extracted with methylenechloride and washed three times with aqueous 80% methanol to remove theexcess 2-allylphenol. This was dried with anhydrous sodium sulfate andthen heated in vacuum at 115° C. to remove the solvent.

Through its NMR, the thus-obtained, phenol-terminated PDMS was found tohave 30 repetitive dimethylsilanoxy units.

PRODUCTION EXAMPLE III-3-2

[Production of Reactive PDMS-B]

This is the same as in Production Example III-3-1, in which, however,73.4 g of eugenol was used in place of 60 g of 2-allylphenol.

Through its NMR, the phenol-terminated PDMS obtained herein was found tohave 30 repetitive dimethylsilanoxy units.

PRODUCTION EXAMPLE III-3-3

[Production of Reactive PDMS-C]

This is the same as in Production Example III-3-1, in which, however,18.1 g of 1,1,3,3-tetramethyldisiloxane was used.

Through its NMR, the phenol-terminated PDMS obtained herein was found tohave 150 repetitive dimethylsilanoxy units.

PRODUCTION EXAMPLE III-4-1

[Production of PC-PDMS Copolymer A₁]

138 g of the reactive PDMS-A obtained in Production Example III-3-1 wasdissolved in 2 liters of methylene chloride, and this was mixed with 10liters of the PC oligomer obtained in the above. To this were added asolution of 26 g of sodium hydroxide in 1 liter of water and 5.7 cc oftriethylamine, and these were reacted by stirring at 500 rpm at roomtemperature for 1 hour.

To the resulting reaction system, added were a solution of 600 g ofbisphenol A dissolved in 5 liters of aqueous 5.2 wt. % sodium hydroxide,8 liters of methylene chloride, and 96 g of p-tert-butylphenol, andthese were reacted by stirring at 500 rpm at room temperature for 2hours.

5 liters of methylene chloride was added to the resulting reactionsystem, which was then washed with 5 liters of water, 5 liters of analkali, 0.03-N sodium hydroxide, 5 liters of an acid, 0.2-N hydrochloricacid, and 5 liters of water (two times) in that order. Finally,methylene chloride was removed from this, and a flaky PC-PDMS copolymerA₁ was obtained. The thus-obtained PC-PDMS copolymer A₁ was dried invacuum at 120° C. for 24 hours. Its viscosity-average molecular weightwas 17,000, and its PDMS content was 3.0% by weight. Theviscosity-average molecular weight and the PDMS content were measured asfollows:

(1) Viscosity-Average Molecular Weight (Mv):

The viscosity of the copolymer in methylene chloride at 20° C. wasmeasured with an Ubbelohde's viscometer, and the intrinsic viscosity [η]thereof was derived from it. The viscosity-average molecular weight (Mv)of the copolymer was calculated according to the following equation:[η]=1.23×10⁻⁵ Mv^(0.83).(2) PDMS Content:

Based on the intensity ratio of the methyl peak of the isopropyl groupof bisphenol A seen at 1.7 ppm in ¹H-NMR of the copolymer to the methylpeak of the dimethylsiloxane moiety seen at 0.2 ppm therein, the PDMScontent of the copolymer was obtained.

PRODUCTION EXAMPLE III-4-2

[Production of PC-PDMS Copolymer A₂]

A flaky PC-PDMS copolymer A₂ was obtained in the same manner as inProduction Example III-4-1, for which, however, 91 g of the reactivePDMS-B was used in place of 138 g of the reactive PDMS-A and 136 g ofp-cumylphenol was used in place of 96 g of p-tert-butylphenol. Itsviscosity-average molecular weight was 16,800, and its PDMS content was2.0% by weight.

PRODUCTION EXAMPLE III-4-3

[Production of PC-PDMS Copolymer A₃]

A flaky PC-PDMS copolymer A₃ was obtained in the same manner as inProduction Example III-4-1, for which, however, the reactive PDMS-C wasused in place of the reactive PDMS-A. Its viscosity-average molecularweight was 17,200, and its PDMS content was 3.0% by weight.

PRODUCTION EXAMPLE III-5-1

[Production of Terminal-modified Polycarbonate B₁]

10 liters of the PC oligomer obtained in Production Example III-2 wasput into a 50-liter reactor equipped with a stirrer, and 249 g of thealkylphenol (a) prepared in Production Example III-1 was dissolvedtherein. Next, aqueous sodium hydroxide solution (sodium hydroxide 53 g,water 1 liter) and 5.8 cc of triethylamine were added thereto andreacted by stirring at 300 rpm for 1 hour. Then, the system was mixedwith a solution of bisphenol A in sodium hydroxide (bisphenol A 720 g,sodium hydroxide 412 g, water 5.5 liters), 8 liters of methylenechloride was added thereto, and these were reacted by stirring at 500rpm for 1 hour. After the reaction, 7 liters of methylene chloride and 5liters of water were added to the system, and stirred at 500 rpm for 10minutes. After stirring was stopped, the system was kept static forphase separation into an organic phase and an aqueous phase. Theresulting organic phase was washed with 5 liters of an alkali (0.03-NNaOH), 5 liters of an acid (0.2-N HCl) and 5 liters of water (twice) inthat order. Next, methylene chloride was evaporated away to obtain aflaky polymer. Its viscosity-average molecular weight was 17,500.

PRODUCTION EXAMPLE III-5-2

[Production of Polycarbonate B₂]

A flaky polymer was obtained in the same manner as in Production ExampleIII-5-1, for which, however, 136 g of p-n-nonylphenol was used in placeof the alkylphenol (a). Its viscosity-average molecular weight was17,400.

PRODUCTION EXAMPLE III-6-1

[Production of Terminal-modified PC-PDMS Copolymer A₄]

46 g of the reactive PDMS-A obtained in Production Example III-3-1 wasdissolved in 2 liters of methylene chloride, and this was mixed with 10liters of the PC oligomer obtained in Production Example III-2. To thiswere added a solution of 26 g of sodium hydroxide in 1 liter of waterand 5.7 cc of triethylamine, and these were reacted by stirring at 500rpm at room temperature for 1 hour.

To the resulting reaction system, added were a solution of 600 g ofbisphenol A dissolved in 5 liters of aqueous 5.2 wt. % sodium hydroxide,8 liters of methylene chloride, and 249 g of the alkylphenol (a), andthese were reacted by stirring at 500 rpm at room temperature for 2hours.

5 liters of methylene chloride was added to the resulting reactionsystem, which was then washed with 5 liters of water, 5 liters of analkali, 0.03-N sodium hydroxide, 5 liters of an acid, 0.2-N hydrochloricacid, and 5 liters of water (two times) in that order. Finally,methylene chloride was removed from this, and a flaky terminal-modifiedPC-PDMS copolymer A₄ was obtained. This was dried in vacuum at 120° C.for 24 hours. Its viscosity-average molecular weight was 17,500, and itsPDMS content was 1.0% by weight.

PRODUCTION EXAMPLE III-6-2

[Production of Terminal-modified PC-PDMS Copolymer A₅]

A flaky terminal-modified PC-PDMS copolymer A₅ was obtained in the samemanner as in Production Example III-6-1, for which, however, 91 g of thereactive PDMS-B was used in place of the reactive PDMS-A. Itsviscosity-average molecular weight was 17,000, and its PDMS content was2.0% by weight.

PRODUCTION EXAMPLE III-6-3

[Production of Terminal-modified PC-PDMS Copolymer A₆]

A flaky terminal-modified PC-PDMS copolymer A₆ was obtained in the samemanner as in Production Example III-6-1, for which, however, 138 g ofthe reactive PDMS-B was used in place of the reactive PDMS-A. Itsviscosity-average molecular weight was 17,000, and its PDMS content was3.0% by weight.

PRODUCTION EXAMPLE III-6-4

[Production of Terminal-modified PC-PDMS Copolymer A₇]

A flaky terminal-modified PC-PDMS copolymer A₇ was obtained in the samemanner as in Production Example III-61, for which, however, the reactivePDMS-B was used in place of the reactive PDMS-A. Its viscosity-averagemolecular weight was 17,100, and its PDMS content was 1.0% by weight.

PRODUCTION EXAMPLE III-6-5

[Production of Terminal-modified PC-PDMS Copolymer A₈]

A flaky terminal-modified PC-PDMS copolymer A₈ was obtained in the samemanner as in Production Example III-6-1, for which, however, thereactive PDMS-C was used in place of the reactive PDMS-A. Itsviscosity-average molecular weight was 17,200, and its PDMS content was1.0% by weight.

PRODUCTION EXAMPLE III-6-6

[Production of PC-PDMS Copolymer A₉]

A flaky PC-PDMS copolymer A₉ was obtained in the same manner as inProduction Example III-6-1, for which, however, 96 g ofp-tert-butylphenol was used in place of the alkylphenol (a) prepared inProduction Example III-1. Its viscosity-average molecular weight was17,000, and its PDMS content was 1.0% by weight.

PRODUCTION EXAMPLE III-6-7

[Production of PC-PDMS Copolymer A₁₀]

A flaky PC-PDMS copolymer A₁₀ was obtained in the same manner as inProduction Example III-6-1, for which, however, 141 g of p-nonylphenolwas used in place of the alkylphenol (a) prepared in Production ExampleIII-1. Its viscosity-average molecular weight was 17,000, and its PDMScontent was 1.0% by weight.

EXAMPLES III-1 TO III-3, AND COMPARATIVE EXAMPLES III-1 TO III-4

The PC-PDMS copolymers A₁ to A₃ and the terminal-modified polycarbonatesB₁ and B₂ that had been prepared in Production Examples, andcommercially-available polycarbonate and PTFE were blended in differentratios as in Table III-1 (in this Table and also in the following TablesIII-2, III-3 and III-4, “Example III-1” is simply designated as “Example1” and the same shall apply to Comparative Examples), fed into a venteddouble-screw extruder (TEM-35B from Toshiba Kikai), kneaded therein at280° C., and then pelletized. The commercially-available polycarbonateis Idemitsu Petrochemical's Toughlon FN1700A (having a viscosity-averagemolecular weight of 17,200); and PTFE is Montefluos' Argoflon F5.

To the compositions of Example III-1 and Comparative Example III-1,added was 0.05 parts by weight of an antioxidant, Asahi Denka Industry'sPEP36 [bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite].

The resulting pellets were dried in hot air at 120° C. for 5 hours.Using Toshiba Kikai's IS100EN (injection-molding machine), the pelletswere molded at 280° C. into test pieces. The mold temperature was 80° C.These test pieces were tested for their combustibility, Izod impactstrength and spiral flow length (SFL) according to the test methodsmentioned below. The test results are given in Table III-2.

(1) Combustibility:

This is based on the UL94 Standard. Samples having a thickness of 1.5 mmare tested for vertical combustion according to Underlighters LaboratorySubject 94.

2) Izod Impact Strength:

Measured according to JIS K 7110. Five samples of the same resincomposition are tested in the same manner and their data are averaged.

(3) SFL:

The pellets are injection-molded to give a melt flow of 2 mm thick. Theinjection pressure is 80 kg/cm² (7.84 MPa), the resin temperature is280° C., and the mold temperature is 80° C.

TABLE III-1 PC-PDMS Terminal- Copolymer modified PC Polycarbonate PTFEamount amount amount PDMS amount type (wt.pts.) type (wt.pts.) (wt.pts.)Content^((*1)) (wt.pts.) Example 1 A₁ 33 B₁ 67 0 1.0 0.3 Example 2 A₂ 50B₁ 50 0 1.0 0.3 Example 3 A₃ 33 B₁ 67 0 1.0 0.3 Comp. Ex. 1 A₁ 33 — 0 671.0 0.3 Comp. Ex. 2 A₂ 50 — 0 50 1.0 0.3 Comp. Ex. 3 A₃ 33 — 0 67 1.00.3 Comp. Ex. 4 A₁ 33 B₂ 67 0 1.0 0.3 Note) ^((*1))This indicates theratio of polyorganosiloxane to the total polycarbonate resin (% byweight).

TABLE III-2 Izod Impact SFL (cm) Combustibility Strength (kJ/m²) Example1 35 V-0 70 Example 2 32 V-0 72 Example 3 35 V-0 71 Comparative Example1 24 V-0 68 Comparative Example 2 22 V-0 67 Comparative Example 3 24 V-069 Comparative Example 4 26 V-0 69

EXAMPLES III-4 TO III-8, AND COMPARATIVE EXAMPLES III-5, III-6

The terminal-modified PC-PDMS copolymers A₄ to A₈ and the PC-PDMScopolymers A₉, A₁₀ that had been prepared in Production Examples, andcommercially-available polycarbonate and PTFE were blended in differentratios as in Table III-3, fed into a vented double-screw extruder(TEM-35B from Toshiba Kikai), kneaded therein at 280° C., and thenpelletized. The commercially-available polycarbonate is IdemitsuPetrochemical's Toughlon FN1700A (having a viscosity-average molecularweight of 17,200); and PTFE is Montefluos' Argoflon F5.

To the compositions of Example III-4 and Comparative Example III-5,added was 0.05 parts by weight of an antioxidant, Asahi Denka Industry'sPEP36 [bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite].

The resulting pellets were dried in hot air at 120° C. for 5 hours.Using Toshiba Kikai's IS100EN (injection-molding machine), the pelletswere molded at 280° C. into test pieces. The mold temperature was 80° C.These test pieces were tested for their combustibility, Izod impactstrength and spiral flow length (SFL) according to the test methodsmentioned above. The test results are given in Table III-4.

TABLE III-3 Terminal- modified PC-PDMS copolymer Polycarbonate PTFEamount amount PDMS amount type (wt.pts.) (wt.pts.) Content ^((*1))(wt.pts.) Example 4 A₄ 100 0 1.0 0.3 Example 5 A₅ 50 50 1.0 0.3 Example6 A₆ 33 67 1.0 0.3 Example 7 A₇ 100 0 1.0 0.3 Example 8 A₈ 100 0 1.0 0.3Comp. Ex. 5 A₉ 100 0 1.0 0.3 Comp. Ex. 6 A₁₀ 100 0 1.0 0.3 Note)^((*1))This indicates the ratio of polyorganosiloxane to the totalpolycarbonate resin (% by weight).

TABLE III-4 Izod Impact SFL (cm) Combustibility Strength (kJ/m²) Example4 40 V-0 70 Example 5 32 V-0 72 Example 6 30 V-0 72 Example 7 39 V-0 69Example 8 39 V-0 70 Comparative Example 5 24 V-0 67 Comparative Example6 26 V-0 67

From Tables III-2 and III-4, it is understood that the samples ofExamples are better than those of Comparative Examples in point of theflowability and the impact resistance.

INDUSTRIAL APPLICABILITY

In its first aspect, the invention provides a colored polycarbonateresin composition of which the advantages are that its flowability isimproved not detracting from the impact resistance of the resinmoldings, and especially the glossiness of the injection moldings of theresin composition is extremely good. Therefore, the polycarbonate resincomposition of the first aspect of the invention is favorable, forexample, to colored parts of electric and electronic appliances,electrically-powered tools and cameras.

In its second aspect, the invention provides a polycarbonate resincomposition which does not contain a halogen or phosphorus-containingflame retardant but contains only minor additives. The impactresistance, the melt flowability and the flame retardancy of the resincomposition and its moldings are all good. In addition, the resincomposition and its moldings are well recyclable because of their goodrecyclability, and the resin composition can be molded into thin-walledand large-sized moldings because of its good moldability. The inventionof this aspect therefore contributes towards solving variousenvironmental problems with plastics and saving natural resources.Accordingly, the invention will expand the applicability ofpolycarbonate resin to electric and electronic appliances includingthose for household use, OA appliances and information appliances and toautomobile parts.

In its third aspect, the invention provides a polycarbonate resincomposition of good flowability, impact resistance and flame retardancy.Accordingly, the resin composition of the third aspect of the inventionis favorable, for example, to the field of electric and electronicappliances (housings, parts).

1. A colored polycarbonate resin composition, comprising: (i) 100 partsby weight of a polycarbonate resin comprising from 10 to 100% by weightof an aromatic polycarbonate (A) having a terminal group of thefollowing general formula (I-1):

wherein R¹ represents a branched alkyl group having from 10 to 35 carbonatoms, and from 0 to 90% by weight of an aromatic polycarbonate (B)having a terminal group of the following general formula (I-2):

wherein R² represents an alkyl group having from 1 to 9 carbon atoms, anaryl group having from 6 to 20 carbon atoms, or a halogen atom, and aindicates an integer of from 0 to 5, and (ii) from 5 to 150 parts byweight of glass fibers (C); (iii) from 100 to 5,000 ppm of a colorant.2. The polycarbonate resin composition as claimed in claim 1, whereinsaid colorant is carbon black.
 3. The polycarbonate resin composition asclaimed in claim 1, wherein the polycarbonate resin has aviscosity-average molecular weight of from 10,000 to 40,000.
 4. Parts ofelectric and electronic appliances, parts of electrically-powered toolsor parts of cameras, comprising: the polycarbonate resin composition ofclaim
 1. 5. The polycarbonate resin composition as claimed in claim 1,wherein component (B) is present in said polycarbonate resin.
 6. Thepolycarbonate resin composition as claimed in claim 1, wherein saidglass fibers have a length of from 0.1 to 8 mm.
 7. The polycarbonateresin composition as claimed in claim 1, wherein said glass fibers havea diameter of from 0.1 to 30 μm.
 8. The polycarbonate resin compositionas claimed in claim 1, wherein said glass fibers are in the form ofrovings, milled fibers, chopped fibers and mixtures thereof.
 9. Thepolycarbonate resin composition as claimed in claim 1, wherein saidglass fibers are surface treated.
 10. The polycarbonate resincomposition as claimed in claim 9, wherein said glass fibers are treatedwith a sizing agent.